KR100575146B1 - Novel substituted phenyl keto enols - Google Patents

Abstract

Spiro-tetrahydropyran-pyrrolinone derivatives (I) are new. They are prepared from new 4-phenylacetylamino-4-alkoxycarbonyl-tetrahydropyran derivatives (II), which in turn, are obtained from new 4-amino-4-alkoxycarbonyl-tetrahydropyran derivatives (XIII), 4-phenylacetylamino-4-carboxy-tetrahydropyran derivatives (XV), 4-amino-4-carboxy-tetrahydropyran derivatives (XVI), 4-amino-4-cyano-tetrahydropyran derivatives (XXII) and 4-cyano-4-phenylacetylamino-tetrahydropyran derivatives (XXIII), substituted phenylacetic acid derivatives (XVII) and substituted phenylacetic acid esters (XVIII). Phenyl-substituted spiro-tetrahydropyran-pyrrolinone derivatives (I) are new: [Image] W' = H; CN; NO 2; halo; alkyl; alkenyl; alkynyl; alkoxy; haloalkyl; haloalkoxy; or optionally substituted phenyl, phenoxy, phenylthio, phenylalkoxy or phenylalkylthio; X = halo; alkyl; alkenyl; alkynyl; alkoxy; alkenyloxy; haloalkyl; haloalkoxy; haloalkenyloxy; CN; NO 2; or optionally substituted phenyl, phenoxy, phenylthio, phenylalkoxy or phenylalkylthio; Y' = H; halo; alkyl; alkoxy; haloalkyl; haloalkoxy; CN; or NO 2; Z' = H; halo; alkyl; alkoxy; haloalkyl; haloalkoxy; OH; CN; NO 2; or optionally substituted phenoxy, phenylthio, phenylalkoxy, phenylalkylthio or 5- or 6-membered heteroaryloxy or heteroarylthio; A = alkyl or optionally substituted phenyl; B' = H or alkyl; G = H; -CO-R 1>; -C(L)-M-R 2>; -SO 2-R 3>; -P(L)(R 4>)(R 5>); E; or -C(L)-NR 6>R 7>; E = metal or ammonium ion; L and M = O or S; R 1>= alkyl, alkenyl, alkoxyalkyl, alkylthioalkyl or polyalkoxyalkyl optio nally substituted with halo or CN; cycloalkyl or heterocyclyl optionally substituted with halo, alkyl or alkoxy; or optionally substituted phenyl, phenylalkyl, heteroaryl, phenoxyalkyl or heteroaryloxy; R 2>= alkyl, alkenyl, alkoxyalkyl or polyalkoxyalkyl optionally substituted with halo or CN; or optionally substituted cycloalkyl, phenyl or benzyl; R 3>, R 4>and R 5>= alkyl, alkoxy, alkylamino, dialkylamino, alkylthio, alkenylthio or cycloalkylthio optionally substituted with halo; or optionally substituted phenyl, benzyl, phenoxy or phenylthio; R 6>and R 7>= H; alkyl, cycloalkyl, alkenyl, alkoxy or alkoxyalkyl optionally substituted with halo or CN; or optionally phenyl or benzyl or NR 6>R 7> [Image] [Image] [Image] [Image] R 8>alkyl; X 1>= F; Cl; or Br; Y 1>= Et; W 1>= H; F; Cl; or Br. ACTIVITY : Insecticidal; acaricidal; nematocidal, herbicidal. MECHANISM OF ACTION : None given.

Description

Newly substituted phenyl keto enols             

The present invention relates to novel phenyl-substituted cyclic ketoenols, numerous methods and intermediates for their preparation, and their use as pesticides and herbicides.

It is already known that certain phenyl-substituted cyclic ketoenols are active as insecticides, acaricides and / or herbicides.

1H-arylpyrrolidine-dione derivatives (see EP-A-456 063, EP-A-521 334, EP-A-596 298, EP-A-613 884, EP-A-613 885, DE-44) 40 594, DE-196 49 665, WO 94/01 997, WO 95/01 358, WO 95/20 572, EP-A-0 668 267, WO 95/26 954, WO 96/25 395, WO 96 / 35 664, WO 97/01 535 and WO 97/02 243) and their use as pesticides and some of them as herbicides.

However, the herbicidal, acaricide and pesticidal activity and / or activity spectrum of these compounds and / or the safety of plants, especially crops, are not always satisfactory.

Thus, the present invention provides compounds of the general formula (I):

In the above formula,             

W represents hydrogen, cyano, nitro, halogen, alkyl, alkenyl, alkynyl, alkoxy, halogenoalkyl or halogenoalkoxy, each optionally substituted phenyl, phenoxy, phenylthio, phenylalkoxy or phenylalkylthio Indicates

X represents halogen, alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, halogenoalkyl, halogenoalkoxy, halogenoalkenyloxy, nitro or cyano, each optionally substituted phenyl, phenoxy, phenyl Thio, phenylalkyloxy or phenylalkylthio;

Y represents hydrogen, halogen, alkyl, alkoxy, halogenoalkyl, halogenoalkoxy, cyano or nitro,

Z represents hydrogen, halogen, alkyl, alkoxy, halogenoalkyl, halogenoalkoxy, hydroxyl, cyano or nitro, or each optionally substituted phenoxy, phenylthio, 5- or 6-membered hetaryl Oxy, 5- or 6-membered hetarylthio, phenylalkyloxy or phenylalkylthio;

A represents alkyl or optionally substituted phenyl,

B represents hydrogen or alkyl,

G represents hydrogen (a) or one of the following radicals:

From here,

E represents a metal ion equivalent or ammonium ion,             

L represents oxygen or sulfur,

M represents oxygen or sulfur,

R ¹ represents alkyl, alkenyl, alkoxyalkyl, alkylthioalkyl or polyalkoxyalkyl, each optionally substituted by halogen or cyano, or cycloalkyl or heterocyclyl, optionally substituted by halogen, alkyl or alkoxy, respectively. Or each optionally substituted phenyl, phenylalkyl, hetaryl, phenoxyalkyl or hetaryloxyalkyl,

R ² each represents alkyl, alkenyl, alkoxyalkyl or polyalkoxyalkyl optionally substituted by halogen or cyano, or each independently cycloalkyl, phenyl or benzyl,

R ³ , R ⁴ and R ⁵ independently of one another each represent alkyl, alkoxy, alkylamino, dialkylamino, alkylthio, alkenylthio or cycloalkylthio optionally substituted by halogen in each occurrence, or each optionally substituted Phenyl, benzyl, phenoxy or phenylthio,

R ⁶ and R ⁷ independently of one another each represent hydrogen, each represents alkyl, cycloalkyl, alkenyl, alkoxy or alkoxyalkyl optionally substituted by halogen or cyano, or each independently represent phenyl or benzyl Or, together with the N atom to which it is attached, form an optionally substituted cycle which optionally contains oxygen or sulfur.

In particular, the compounds of the general formula (I) may exist as optical mixtures, or as mixtures of isomers of different compositions, which can be separated by conventional methods as necessary, depending on the nature of the substituents. Pure isomers and isomer mixtures, methods for their preparation and use, and compositions containing them, are all subject to patents of the present invention. However, for convenience, the following will always refer to compounds of the general formula (I), but this also means pure compounds and mixtures with optionally different ratios of isomeric compounds.

When the various meanings (a), (b), (c), (d), (e), (f) and (g) of the group G are included, the following main structures (Ia) to (Ig) are obtained. :

Wherein A, B, E, L, M, W, X, Y, Z, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each as defined above.

It has also been found that according to the invention the novel compounds of general formula (I) are obtained by one of the methods described below:

(A) A compound of formula (I-a) is obtained by intramolecular condensation of a compound of formula (II) in the presence of a diluent and in the presence of a base:

Where             

A, B, W, X, Y and Z are each as defined above,

R ⁸ represents alkyl (preferably C ₁ -C ₆ -alkyl).

(B) Compounds of the general formula (Ib) wherein R ¹ , A, B, W, X, Y and Z are each as defined above are compounds of the general formula (Ia) as defined above, wherein A, B, W , X, Y and Z are each as defined above), optionally in the presence of a diluent and optionally in the presence of an acid binder

    α) is reacted with an acyl halide of the general formula (III)

    β) is obtained by reacting with a carboxylic anhydride of the general formula (IV) below;

Where

R ¹ is as defined above,

Hal is halogen (especially chlorine or bromine)

(C) Compounds of formula (Ic) wherein R ² , A, B, W, M, X, Y and Z are as defined above and L represents oxygen, respectively, Wherein A, B, W, X, Y and Z are each as defined above), optionally in the presence of a diluent and optionally in the presence of an acid binder a chloroformic ester of the general formula (V) Or obtained by reacting with chloroformic acid thioesters;

Where

R ² and M are each as defined above.

(D) Compounds of formula (Ic) wherein R ² , A, B, W, M, X, Y and Z are as defined above and L represents sulfur are those of the formula (Ia) In which A, B, W, X, Y and Z are each as defined above), optionally in the presence of a diluent and optionally in the presence of an acid binder, chloromonothioformic acid of formula (VI) Obtained by reacting with an ester or chlorodithioformic acid ester;

Where

M and R ² are each as defined above.

(E) Compounds of the general formula (Id) wherein R ³ , A, B, W, X, Y and Z are each as defined above are compounds of the general formula (Ia) as defined above, wherein A, B, W , X, Y and Z are each as defined above) by reaction with sulfonyl chlorides of the general formula (VII) below, optionally in the presence of a diluent and optionally in the presence of an acid binder;

Where

R ³ is as defined above.

(F) A compound of formula (Ie) wherein L, R ⁴ , R ⁵ , A, B, W, X, Y and Z are each as defined above, is a compound of formula (Ia) A, B, W, X, Y and Z are each as defined above) by reacting with a phosphorus compound of the general formula (VIII) below in the presence of a diluent and optionally in the presence of an acid binder Or;

Where

L, R ⁴ and R ⁵ are each as defined above,

Hal represents halogen (especially chlorine or bromine).

(G) Compounds of formula (If) wherein E, A, B, W, X, Y and Z are each as defined above are compounds of formula (Ia), wherein A, B, W, X, Y and Z are each as defined above), optionally obtained by reacting with a metal compound or amine of the general formula (IX) or (X) in the presence of a diluent;

Where             

Me represents a monovalent or divalent metal (preferably an alkali or alkaline earth metal, for example lithium, sodium, potassium, magnesium or calcium),

t represents a number of 1 or 2,

R ⁹ , R ¹⁰ and R ¹¹ independently of each other represent hydrogen or alkyl (preferably C ₁ -C ₈ -alkyl).

(H) A compound of formula (Ig) wherein L, R ⁶ , R ⁷ , A, B, W, X, Y and Z are each as defined above is a compound of formula (Ia) A, B, W, X, Y and Z are as defined above, respectively,

α) optionally react with an isocyanate or isothiocyanate of the general formula (XI) in the presence of a diluent and optionally in the presence of a catalyst, or

β) It has been found to be obtained by reacting carbamoyl chloride or thiocarbamoyl chloride of the general formula (XII) in the presence of a diluent and optionally in the presence of an acid binder:

Where

R ⁶ , L and R ⁷ are each as defined above.

It has also been found in accordance with the invention that the novel compounds of general formula (I) have very good activity as pesticides, preferably insecticides, acaricides and herbicides, and are very good in plants, in particular in crop tolerability.

Formula (I) provides a general definition of a compound according to the invention. The range of preferred substituents and / or radicals listed in the general formulas mentioned above and hereinafter are shown below:

W is preferably hydrogen, nitro, cyano, halogen, C ₁ -C ₆ -alkyl, C ₂ -C ₆ -alkenyl, C ₂ -C ₆ -alkynyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₄ -halogenoalkyl or C ₁ -C ₄ -halogenoalkoxy,

X is preferably halogen, C ₁ -C ₆ -alkyl, C ₂ -C ₆ -alkenyl, C ₂ -C ₆ -alkynyl, C ₁ -C ₆ -alkoxy, C ₃ -C ₆ -alkenyloxy , C ₁ -C ₄ -halogenoalkyl, C ₁ -C ₄ -halogenoalkoxy, C ₂ -C ₆ -halogenoalkenyloxy, cyano or nitro, or halogen, C ₁ -C _6- Phenyl, phenoxy, phenylthio, phenyl-C, optionally substituted by alkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₄ -halogenoalkyl, C ₁ -C ₄ -halogenoalkoxy, nitro or cyano _1- C ₄ -alkoxy or phenyl-C ₁ -C ₄ -alkylthio;

Y preferably represents hydrogen, halogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₄ -halogenoalkyl, C ₁ -C ₄ -halogenoalkoxy, cyano or nitro Indicates,

Z is preferably hydrogen, halogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₄ -halogenoalkyl, C ₁ -C ₄ -halogenoalkoxy, hydroxyl, cyano Or nitro or halogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -halogenoalkyl, C ₁ -C ₄ -halogenoalkoxy, nitro or cyano, respectively Phenoxy, phenylthio, thiazolyloxy, pyridinyloxy, pyrimidyloxy, pyrazolyloxy, phenyl-C ₁ -C ₄ -alkoxy or phenyl-C ₁ -C ₄ -alkylthio optionally substituted by

A preferably represents C ₁ -C ₆ -alkyl or phenyl optionally substituted by halogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, nitro or cyano,

B preferably represents hydrogen or C ₁ -C ₆ -alkyl,

G preferably represents hydrogen (a) or one of the following radicals:

From here,

E represents a metal ion equivalent or ammonium ion,

L represents oxygen or sulfur,

M represents oxygen or sulfur,             

R ¹ is preferably C ₁ -C ₂₀ -alkyl, C ₂ -C ₂₀ -alkenyl, C ₁ -C ₈ -alkoxy-C ₁ -C ₈ -alkyl, each optionally substituted by halogen or cyano ₁ -C ₈ - alkylthio -C ₁ -C ₈ - alkyl or poly -C ₁ -C ₈ - alkoxy -C ₁ -C ₈ - hana represent alkyl, or optionally it is not directly adjacent or two methylene groups are C ₃ -C ₈ -cycloalkyl substituted by oxygen and / or sulfur and optionally substituted by halogen, C ₁ -C ₆ -alkyl or C ₁ -C ₆ -alkoxy, or

Halogen, cyano, nitro, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₆ -halogenoalkyl, C ₁ -C ₆ -halogenoalkoxy, C ₁ -C ₆ -alkyl Phenyl optionally substituted by thio or C ₁ -C ₆ -alkylsulfonyl, or

Phenyl-C optionally substituted by halogen, nitro, cyano, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₆ -halogenoalkyl or C ₁ -C ₆ -halogenoalkoxy _1- C ₆ -alkyl, or

5- or 6-membered hetaryl (eg pyrazolyl, thiazolyl) optionally substituted by halogen or C ₁ -C ₆ -alkyl and having one or two hetero atoms selected from the group consisting of oxygen, sulfur and nitrogen , Pyridyl, pyrimidyl, furanyl or thienyl), or

Phenoxy-C ₁ -C ₆ -alkyl optionally substituted by halogen or C ₁ -C ₆ -alkyl, or

5- or 6-membered hetaryloxy-C ₁ -C ₆ -optionally substituted by halogen, amino or C ₁ -C ₆ -alkyl and having one or two hetero atoms selected from the group consisting of oxygen, sulfur and nitrogen Alkyl (eg, pyridyloxy-C ₁ -C ₆ -alkyl, pyrimidyloxy-C ₁ -C ₆ -alkyl or thiazolyloxy-C ₁ -C ₆ -alkyl),

R ² is preferably C ₁ -C ₂₀ -alkyl, C ₂ -C ₂₀ -alkenyl, C ₁ -C ₈ -alkoxy-C ₂ -C ₈ -alkyl or poly, each optionally substituted by halogen or cyano -C ₁ -C ₈ -alkoxy-C ₂ -C ₈ -alkyl, or

C ₃ -C ₈ -cycloalkyl optionally substituted by halogen, C ₁ -C ₆ -alkyl or C ₁ -C ₆ -alkoxy, or

Phenyl optionally substituted by halogen, cyano, nitro, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₆ -halogenoalkyl or C ₁ -C ₆ -halogenoalkoxy, respectively, or Benzyl,

R ³ preferably represents C ₁ -C ₈ -alkyl optionally substituted by halogen, or halogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₄ -halogeno, respectively Phenyl or benzyl optionally substituted by alkyl, C ₁ -C ₄ -halogenoalkoxy, cyano or nitro,

R ⁴ and R ⁵ are preferably independently of each other, in each case C ₁ -C ₈ -alkyl, C ₁ -C ₈ -alkoxy, C ₁ -C ₈ -alkylamino, di- ( C ₁ -C ₈ -alkyl) amino, C ₁ -C ₈ -alkylthio or C ₃ -C ₈ -alkenylthio or each halogen, nitro, cyano, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ - halogenoalkyl alkoxy, C ₁ -C ₄ - alkylthio, C ₁ -C ₄ - halogenoalkyl alkylthio, C ₁ -C ₄ - alkyl or C ₁ -C ₄ - alkyl optionally substituted by halogeno Phenyl, phenoxy or phenylthio,

R ⁶ and R ⁷ are preferably each represents a hydrogen, or, respectively, by halogen or cyano, optionally substituted independently of one another C ₁ -C ₈ - alkyl, C ₃ -C ₈ - cycloalkyl, C ₁ -C ₈ -Alkoxy, C ₃ -C ₈ -alkenyl or C ₁ -C ₈ -alkoxy-C ₂ -C ₈ -alkyl or each independently halogen, C ₁ -C ₈ -alkyl, C ₁ -C ₈ -halogeno alkyl, or C ₁ -C ₈ - alkoxy by optionally substituted phenyl or benzyl, or represent, together, optionally one methylene group is replaced by oxygen or sulfur, C ₁ -C ₆ - alkyl optionally substituted by a C ₃ -C ₆ -alkylene radical.

W is particularly preferably hydrogen, nitro, cyano, fluorine, chlorine, bromine, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₂ -halogenoalkyl or C ₁ -C ₂ Halogenoalkoxy,

X is particularly preferably fluorine, chlorine, bromine, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₃ -C ₄ -alkenyloxy, C ₁ -C ₂ -halogenoalkyl, C ₁ -C ₂ -halogenoalkoxy, C ₂ -C ₄ -halogenoalkenyloxy, cyano or nitro or each represent fluorine, chlorine, bromine, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy , C ₁ -C ₂ -halogenoalkyl, C ₁ -C ₂ -halogenoalkoxy, nitro or cyano optionally substituted with phenyl or benzyloxy,

Y is particularly preferably hydrogen, fluorine, chlorine, bromine, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₂ -halogenoalkyl, C ₁ -C ₂ -halogenoalkoxy, Represents cyano or nitro,

Z is particularly preferably hydrogen, fluorine, chlorine, bromine, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₂ -halogenoalkyl, C ₁ -C ₂ -halogenoalkoxy, Hydroxyl, cyano or nitro, or fluorine, chlorine, bromine, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₂ -halogenoalkyl, C ₁ -C _2- Phenoxy or benzyloxy optionally substituted by halogenoalkoxy, nitro or cyano,

A particularly preferably represents C ₁ -C ₄ -alkyl or phenyl,

B particularly preferably represents hydrogen, methyl or ethyl,

G particularly preferably represents hydrogen (a) or one of the following radicals (particularly (a), (b) or (c)):

From here,

E represents a metal ion equivalent or ammonium ion,

L represents oxygen or sulfur,             

M represents oxygen or sulfur,

R ¹ is particularly preferably C ₁ -C ₁₆ -alkyl, C ₂ -C ₁₆ -alkenyl, C ₁ -C ₆ -alkoxy-C ₁ -C ₆ -alkyl, C, each optionally substituted by fluorine or chlorine, respectively ₁ -C ₆ - alkylthio -C ₁ -C ₆ - alkyl or poly -C ₁ -C ₆ - alkoxy -C ₁ -C ₆ - hana represent alkyl, or optionally it is not directly adjacent or two methylene groups are C ₃ -C ₇ -cycloalkyl substituted by oxygen and / or sulfur and optionally substituted by fluorine, chlorine, C ₁ -C ₅ -alkyl or C ₁ -C ₅ -alkoxy, or

Fluorine, chlorine, bromine, cyano, nitro, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₃ -halogenoalkyl, C ₁ -C ₃ -halogenoalkoxy, C _1- C ₄ - alkylthio or C ₁ -C ₄ - or represents a phenyl optionally substituted by alkyl sulfonyl,

Phenyl-C ₁ optionally substituted by fluorine, chlorine, bromine, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₃ -halogenoalkyl or C ₁ -C ₃ -halogenoalkoxy -C ₄ -alkyl or

Each represents pyrazolyl, thiazolyl, pyridyl, pyrimidyl, furanyl or thienyl, optionally substituted by fluorine, chlorine, bromine or C ₁ -C ₄ -alkyl,

Phenoxy-C ₁ -C ₅ -alkyl optionally substituted by fluorine, chlorine, bromine or C ₁ -C ₄ -alkyl, or

Each fluorine, chlorine, bromine, amino or C ₁ -C ₄ - alkyl optionally substituted by a pyridyloxy -C ₁ -C ₅ - alkyl, pyrimidyl-oxy -C ₁ -C ₅ - alkyl or thiazolyl oxy -C _1- C ₅ -alkyl,

R ² is particularly preferably C ₁ -C ₁₆ -alkyl, C ₂ -C ₁₆ -alkenyl, C ₁ -C ₆ -alkoxy-C ₂ -C ₆ -alkyl or poly, optionally substituted by fluorine or chlorine, respectively -C ₁ -C ₆ -alkoxy-C ₂ -C ₆ -alkyl, or

C ₃ -C ₇ -cycloalkyl optionally substituted by fluorine, chlorine, C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxy, or

Optionally by fluorine, chlorine, bromine, cyano, nitro, C ₁ -C ₄ -alkyl, C ₁ -C ₃ -alkoxy, C ₁ -C ₃ -halogenoalkyl or C ₁ -C ₃ -halogenoalkoxy, respectively Substituted phenyl or benzyl,

R ³ particularly preferably represents C ₁ -C ₆ -alkyl optionally substituted by fluorine or chlorine, or is fluorine, chlorine, bromine, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₂ - halogenoalkyl alkoxy, C ₁ -C ₂ - halogenoalkyl, cyano, or represents an optionally substituted phenyl or benzyl by nitro,

R ⁴ and R ⁵ are particularly preferably independently of each other C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₆ -alkylamino, each optionally substituted with fluorine or chlorine in each case, Di- (C ₁ -C ₆ -alkyl) amino, C ₁ -C ₆ -alkylthio or C ₃ -C ₄ -alkenylthio, or represent fluorine, chlorine, bromine, nitro, cyano, C _1- C ₃ -alkoxy, C ₁ -C ₃ -halogenoalkoxy, C ₁ -C ₃ -alkylthio, C ₁ -C ₃ -halogenoalkylthio, C ₁ -C ₃ -alkyl or C ₁ -C ₃ -halo Phenyl, phenoxy or phenylthio optionally substituted by genoalkyl,

R ⁶ and R ⁷ particularly preferably independently of each other represent hydrogen or each independently substituted with fluorine or chlorine, C ₁ -C ₆ -alkyl, C ₃ -C ₆ -cycloalkyl, C ₁ -C ₆ -Alkoxy, C ₃ -C ₆ -alkenyl or C ₁ -C ₆ -alkoxy-C ₂ -C ₆ -alkyl or each represent fluorine, chlorine, bromine, C ₁ -C ₅ -halogenoalkyl, C ₁ -C ₅ - alkyl or C ₁ -C ₅ - or represent optionally substituted phenyl or benzyl, with an alkoxy, with optionally one methylene group is replaced by oxygen or sulfur, C ₁ -C ₄ - alkyl, optionally by Substituted C ₃ -C ₆ -alkylene radicals.

In the radical definitions referred to as (particularly) preferred, halogens (e.g. in halogenoalkyl, halogenoalkoxy or halogenoalkenyloxy) combined with other radicals are particularly fluorine, chlorine and bromine, more particularly fluorine and chlorine. Indicates.

W is very particularly preferably hydrogen, nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, methoxy, ethoxy, n-propoxy, iso Propoxy, trifluoromethyl, difluoromethoxy, trifluoromethoxy,

X is very particularly preferably fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, methoxy, ethoxy, n-propoxy, isopropoxy, trifluoro Methyl, trifluoromethoxy, difluoromethoxy, nitro or cyano,

Y is very particularly preferably hydrogen, fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, methoxy, ethoxy, n-propoxy, isoprop Foxy, trifluoromethyl, trifluoromethoxy, difluoromethoxy, nitro or cyano,

Z is very particularly preferably hydrogen, fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, methoxy, ethoxy, n-propoxy, isoprop Foxy, trifluoromethyl, trifluoromethoxy, difluoromethoxy, nitro or cyano,

A very particularly preferably represents methyl or ethyl,

B very particularly preferably represents hydrogen or methyl,

G very particularly preferably represents hydrogen (a) or one of the following radicals (particularly (a), (b) or (c)):

From here,

E represents a metal ion equivalent or ammonium ion,             

L represents oxygen or sulfur,

M represents oxygen or sulfur,

R ¹ is very particularly preferably C ₁ -C ₁₄ -alkyl, C ₂ -C ₁₄ -alkenyl, C ₁ -C ₄ -alkoxy-C ₁ -C ₆ -alkyl, each optionally substituted by fluorine or chlorine, C ₁ -C ₄ -alkylthio-C ₁ -C ₆ -alkyl or poly-C ₁ -C ₄ -alkoxy-C ₁ -C ₄ -alkyl, or

One or two methylene groups, optionally not directly adjacent, are replaced by oxygen and / or sulfur and substituted with fluorine, chlorine, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, C ₃ -C ₆ -cycloalkyl optionally substituted by methoxy, ethoxy, n-propoxy or isopropoxy, or

Fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n-propyl, i-propyl, methoxy, ethoxy, trifluoromethyl, trifluoromethoxy, methylthio, ethylthio, methylsulfonyl or ethyl Phenyl optionally substituted by sulfonyl, or

Benzyl optionally substituted by fluorine, chlorine, bromine, methyl, ethyl, n-propyl, i-propyl, methoxy, ethoxy, trifluoromethyl or trifluoromethoxy, or

Each represent furanyl, thienyl or pyridyl optionally substituted by fluorine, chlorine, bromine, methyl or ethyl, or

Phenoxy-C ₁ -C ₄ -alkyl optionally substituted by fluorine, chlorine, methyl or ethyl, or

Each fluorine, chlorine, amino, methyl or ethyl optionally substituted by pyridyloxy -C ₁ -C ₄ - alkyl, pyrimidyl-oxy -C ₁ -C ₄ - alkyl or thiazolyl oxy -C ₁ -C ₄ - alkyl, ,

R ² is very particularly preferably C ₁ -C ₁₄ -alkyl, C ₂ -C ₁₄ -alkenyl, C ₁ -C ₄ -alkoxy-C ₂ -C ₆ -alkyl, each optionally substituted by fluorine or chlorine, or Poly-C ₁ -C ₄ -alkoxy-C ₂ -C ₆ -alkyl, or

C ₃ -C ₆ -cycloalkyl optionally substituted by fluorine, chlorine, methyl, ethyl, n-propyl, isopropyl or methoxy, or

Phenyl or benzyl, each optionally substituted by fluorine, chlorine, cyano, nitro, methyl, ethyl, n-propyl, i-propyl, methoxy, ethoxy, trifluoromethyl or trifluoromethoxy,

R ³ very particularly preferably represents methyl, ethyl, n-propyl, isopropyl, n-butyl or t-butyl, each optionally substituted by fluorine or chlorine,

Phenyl or benzyl, optionally substituted by fluorine, chlorine, bromine, methyl, ethyl, isopropyl, t-butyl, methoxy, ethoxy, isopropoxy, trifluoromethyl, trifluoromethoxy, cyano or nitro, respectively ,

R ⁴ and R ⁵ are very particularly preferably independently of each other C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylamino, each optionally substituted by fluorine or chlorine in each case , Di- (C ₁ -C ₄ -alkyl) amino or C ₁ -C ₄ -alkylthio, or

Each represent phenyl, phenoxy or phenylthio optionally substituted by fluorine, chlorine, bromine, nitro, cyano, methyl, methoxy, trifluoromethyl or trifluoromethoxy,

R ⁶ and R ⁷ very particularly preferably independently of each other represent hydrogen, or each independently substituted with fluorine or chlorine, C ₁ -C ₄ -alkyl, C ₃ -C ₆ -cycloalkyl, C ₁ -C ₄ -alkoxy, C ₃ -C ₄ -alkenyl or C ₁ -C ₄ -alkoxy-C ₂ -C ₄ -alkyl, or

Each represent phenyl or benzyl, optionally substituted by fluorine, chlorine, bromine, methyl, methoxy or trifluoromethyl,

Together, they represent C ₅ -C ₆ -alkylene radicals, optionally with one methylene group replaced by oxygen or sulfur and optionally substituted by methyl or ethyl.

Particular preference is given to compounds of the general formula (I) mentioned above, wherein A represents CH ₃ , B represents hydrogen and in particular G is very particularly preferred.

The definitions or explanations of the general or preferred radicals mentioned above can be combined with one another if necessary, ie a combination between the range and the preferred range is possible. This applies to the final product and corresponding starting materials and intermediates.

Preference is given to compounds of the formula (I) which comprise a combination of the definitions mentioned above as being preferred.             

Particular preference is given to compounds of the formula (I) which comprise a combination of the definitions mentioned above as particularly preferred.

Very particular preference is given to compounds of the formula (I) which comprise a combination of the definitions mentioned above as very particularly preferred.

Saturated or unsaturated hydrocarbon radicals, such as alkyl or alkenyl, including those bonded with heteroatoms such as, for example, alkoxy, are in each case as straight or branched as possible.

The optionally substituted radical may be mono- or polysubstituted, and when polysubstituted, the substituents may be the same or different.

In addition to the compounds mentioned in the preparation examples, compounds of the general formula (I-a) may be specifically mentioned:             

Table 1

When N-[(4-chloro-2,6-dimethyl) -phenylacetyl] -4-amino-4-carboxyethyl-2-methyl-tetrahydropyran is used as a starting material according to method (A), The process of the method according to the invention can be represented by the following scheme:

According to Method (Bα), 3-[(2-chloro-4-methyl) -phenyl] -5,5-[(2-ethyl) -ethyleneoxyethyl] -pyrrolidine-2,4-dione and py When using baloyl chloride as starting material, the process of the process according to the invention can be represented by the following scheme:             

According to Method (Bβ), 3-[(2,4-dichloro) -phenyl] -5,5-[(2-methyl) -ethyleneoxyethyl] -pyrrolidine-2,4-dione and acetic anhydride When used as starting material, the process of the process according to the invention can be represented by the following scheme:

According to method (C), 8-[(2,4-dichloro) -phenyl] -5,5-[(2-methyl) -ethyleneoxyethyl] -pyrrolidine-2,4-dione and ethoxyethyl When using chloroformate as starting material, the process of the process according to the invention can be represented by the following scheme:

According to method (D), 3-[(2,6-dibromo-4-methyl) -phenyl] -5,5-[(2-ethyl) -ethyleneoxyethyl] -pyrrolidine-2, When 4-dione and methyl chloromonothioformate are used as starting materials, the process of the process according to the invention can be represented by the following scheme:

According to method (E), 3-[(2,4,6-trimethyl) -phenyl] -5,5-[(2-methyl) -ethyleneoxyethyl] -pyrrolidine-2,4-dione and methane When using sulfonyl chloride as starting material, the process of the process according to the invention can be represented by the following scheme:

According to method (F), 3-[(4-bromo-2-chloro-6-methyl) -phenyl] -4-hydroxy-5,5-[(2-methyl) -ethylenedioxyethyl]- When pyrrolidine-2,4-dione and (2,2,2-trifluoroethyl) methanethio-phosphonyl chloride are used as starting materials, the process of the method according to the present invention is represented by the following scheme. Can be broken:

According to method (G), 3-[(2,4-dichloro) -6-methylphenyl] -5,5-[(2-ethyl) -ethylenedioxyethyl] -pyrrolidine-2,4-dione and When NaOH is used as the reaction component, the process of the method according to the invention can be represented by the following scheme:

According to method (Hα), 3-[(2-chloro-4-bromo-5-methyl) -phenyl] -4-hydroxy-5,5-[(2-methyl) -ethyleneoxyethyl] -pi In the case of using lollidine-2,4-dione and ethyl isocyanate as starting materials, the process of the process according to the invention can be represented by the following scheme:

According to Method (Hβ), 3-[(2-chloro-4,6-dimethyl) -phenyl] -5,5-[(2-methyl) -ethylenedioxyethyl] -pyrrolidine-2,4- When using dione and dimethylcarbamoyl chloride as starting materials, the process of the process according to the invention can be represented by the following scheme:             

The compounds of formula (II) which are required as starting materials for process (A) according to the invention are novel:

Where

A, B, W, X, Y, Z and R ⁸ are each as defined above.

Acylamino acid esters of formula (II) are for example acylated with amino acid derivatives of formula (XIII) with substituted phenylacetyl halides of formula (XIV) (see Chem. Reviews 52 , 237-). 416 (1953); Bhattacharya, Indian J. Chem. 6 , 341-5, 1968), obtained by esterifying acylamino acids of the general formula (XV), Chem. Ind. (London) 1568 (1968) ):

Where

A, B, R ⁸ , W, X, Y and Z are as defined above, respectively.

Hal represents chlorine or bromine.

Compounds of general formula (XV) are novel:

Where

A, B, W, X, Y and Z are as defined above, respectively.

Compounds of the general formula (XV) include, for example, 4-amino-tetrahydropyran-4-carboxylic acid of the following general formula (XVI) by Schotten-Baumann (Organikum, VEB Deutscher Verlag der Wissenschaften, Berlin 1977, p. 505) to obtain acylation with substituted phenylacetyl halides of the general formula (XIV):             

Where

A, B, W, X, Y and Z are each as defined above,

Hal represents chlorine or bromine.

Some of the compounds of formula (XIV) are novel and can be prepared by known methods (see, eg, DE-196 49 665).

Compounds of general formula (XIV) are, for example, substituted phenylacetic acid of general formula (XVII) in the presence of a diluent (optionally chlorinated aliphatic or aromatic hydrocarbons such as, for example, toluene or methylene chloride) By reaction with a halogenating agent (e.g. thionyl chloride, thionyl bromide, oxalyl chloride, phosgene, phosphorus trichloride, phosphorus tribromide or phosphorus pentachloride) at a temperature of -20 to 150 ° C, preferably -10 to 100 ° C Is obtained:

Wherein W, X, Y and Z are each as defined above.             

Some of the compounds of formula (XVII) are novel and can be prepared by methods known in the Organikum 15th edition, p. 533, VEB Deutscher Verlag der Wissenschaften, Berlin 1977, DE 196 49 665. have.

Compounds of general formula (XVII) can be prepared by, for example, substituted phenylacetic acid esters of the general formula (XVIII) with acids (for example inorganic acids such as hydrochloric acid) or bases (for example alkali metals such as sodium hydroxide or potassium hydroxide). Hydroxide) in the presence of a diluent (for example an aqueous alcohol such as methanol or ethanol) and optionally hydrolysis at a temperature of 0 to 150 ° C, preferably 20 to 100 ° C:

Where

W, X, Y, Z and R ⁸ are each as defined above.

Some of the compounds of formula (XVIII) are novel and can be prepared by methods of known principle.

Compounds of general formula (XVIII) are for example substituted 1,1,1-trichloro-2-phenylethane of general formula (XIX) in the presence of a diluent (for example an alcohol derived from alkoxide) React with an alkoxide (for example an alkali metal alkoxide such as sodium methoxide or sodium ethoxide) at a temperature of 0 to 150 ° C., preferably 20 to 120 ° C., followed by -20 to 150 ° C., preferably 0 to 100 Obtained by reaction with an acid (for example an inorganic acid such as sulfuric acid) at a temperature of DEG C (DE-3 314 249):

Wherein W, X, Y and Z are each as defined above.

Some of the compounds of formula (XIX) are novel and can be prepared by methods of known principle.

Compounds of the general formula (XIX) are, for example, aniline of the following general formula (XX), in the presence of alkyl nitrite of the general formula (XXI), in the presence of copper (II) chloride and optionally Obtained by reaction with vinylidene chloride (CH ₂ = CCl ₂ ) at a temperature of -20 to 80 ° C., preferably 0 to 60 ° C., in the presence of an aliphatic nitrile such as acetonitrile):

Where

W, X, Y and Z are as defined above, respectively,

R ¹³ represents alkyl, preferably C ₁ -C ₆ -alkyl.

Some of the compounds of formula (XX) are known. These can be prepared by methods known in the literature, for example by reducing the corresponding nitro compound or by halogenating aniline or acetanilide and then reisolating.

Compounds of general formula (XXI) are known compounds of organic chemistry. Copper (II) chloride and vinylidene chloride have been known for a long time and are commercially available.

Substituted cyclic aminocarboxylic acids of the general formula (XVI) can generally be obtained by Bucherer-Bergs synthesis or by Strecker synthesis, which in each case are different isomeric forms in these synthesis Is obtained. Thus, under the conditions of the Bucher-Berg's synthesis, isomers (hereinafter simply referred to as β) in which the radicals R and the carboxyl groups are in the equilateral position are mainly obtained, whereas under the conditions of the Straker synthesis, amino groups and radicals are obtained. Isomers in which R is in the horizontal position (hereinafter simply referred to as α) are mainly obtained:

  Boucher-Berg's Synthesis (β Isomers) Stacker Synthesis (α Isomers)

Compounds of formulas (XIII) and (XVI) are novel. They can be prepared by known methods (see, eg, Compagnon, Ann. Chim. (Paris) [14] 5, p. 11-22, 23-27 (1970), L. Munday, J. Chem. Soc. 4372 (1961); JT Eward, C. Jitrangeri, Can.J. Chem. 53, 3339 (1975)).

In addition, the starting material of formula (II) used in the above method (A) may be reacted with the aminonitrile of formula (XXII) by substituted phenylacetyl halide of formula (XIV). After obtaining, it can be prepared by decomposing the acid alcohol:

Where

A, B, W, X, Y, Z, R ⁸ and Hal are each as defined above.

Compounds of general formula (XXIII) are also novel. Compounds of general formula (XXII) are also novel.             

Acyl halides of general formula (III), which are further needed as starting materials for carrying out the processes (B), (C), (D), (E), (F), (G) and (H) according to the invention, Carboxylic anhydride of formula (IV), chloroformic acid ester or chloroformic acid thioester of formula (V), chloromonothioformic acid ester or chlorodithioformic acid ester of formula (VI), sulfonyl of formula (VII) Chloride, phosphorus compounds of formula (VIII), metal hydroxides of formulas (IX) and (X), metal alkoxides or amines, isocyanates of formula (XI) and carbamoyl chlorides of formula (XII) are organic or inorganic Compounds generally known in chemistry.

In addition, compounds of the general formulas (XIV), (XVII), (XVIII), (XIX) and (XX) may be prepared by the methods described in and / or described in the patent applications cited above. (See DE-196 49 665 and German Patent Application No. 19613171.5 of the applicant, filed on April 2, 1996 and not yet published).

Method (A) is characterized in that A, B, W, X, Y, Z and R ⁸ each condensate intramolecularly a compound of formula (II) as defined above in the presence of a diluent and in the presence of a base do.

Suitable diluents for process (A) according to the invention are all organic solvents which are inert to the reactants. These preferably include hydrocarbons such as toluene and xylene, ethers such as dibutyl ether, tetrahydrofuran, dioxane, glycol dimethyl ether and diglycol dimethyl ether, further polar solvents such as Dimethyl sulfoxide, sulfolane, dimethylformamide and N-methylpyrrolidone, and also alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol and t-butanol are used.

Suitable bases (deprotonating agents) for use in carrying out process (A) according to the invention are all conventional proton acceptors. As these, it is preferable to use alkali metal and alkaline earth metal oxides, hydroxides and carbonates such as sodium hydroxide, potassium hydroxide, magnesium oxide, calcium oxide, sodium carbonate, potassium carbonate and calcium carbonate, which are also used as phase transfer catalysts, For example, triethylbenzylammonium chloride, tetrabutylammonium bromide, adogen 464 (= methyltrialkyl (C ₈ -C ₁₀ ) ammonium chloride) or TDA 1 (= tris (methoxyethoxyethyl) -amine) Can be used under the following conditions. Alkali metals such as sodium or potassium may also be used. In addition, alkali metal and alkaline earth metal amides and hydrides such as sodium amide, sodium hydride and calcium hydride, and further also alkali metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide Can be used.

When carrying out process (A) according to the invention, the reaction temperature can vary within a relatively wide range. In general, the reaction is carried out at temperatures between -75 and 200 ° C, preferably between -50 and 150 ° C.

Process (A) according to the invention is generally carried out under atmospheric pressure.

When carrying out the process (A) according to the invention, the reactive component and the deprotonated base of the general formula (II) are generally used in approximately equimolar amounts to twice the molar amount. However, it is also possible to use one component or another component in a large excess (3 mol or less).

Method (Bα) is characterized by reacting a compound of general formula (I-a) with a carbonyl halide of general formula (III), optionally in the presence of a diluent and in the presence of an acid binder.

Suitable diluents for use in the process (Bα) according to the invention are all solvents which are inert to acyl halides. These include hydrocarbons such as benzine, benzene, toluene, xylene and tetralin, also halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, and also ketones, for example Acetone and methyl isopropyl ketone, further ethers such as diethyl ether, tetrahydrofuran and dioxane, carboxylic acid esters such as ethyl acetate, and strongly polar solvents such as dimethylformamide , Dimethyl sulfoxide and sulfolane are preferably used. If the acyl halide is stable against hydrolysis, the reaction may also be carried out in the presence of water.

Suitable acid binders for the reaction of the process (Bα) according to the invention are all customary acid acceptors. These are preferably tertiary amines such as triethylamine, pyridine, diazabicyclooctane (DABCO), diazabicycloundecene (DBU), diazabicyclononene (DBN), Huenig bases. And N, N-dimethyl-aniline, further alkaline earth metal oxides such as magnesium oxide and calcium oxide, also alkali metal and alkaline earth metal carbonates such as sodium carbonate, potassium carbonate and calcium carbonate, and also alkali metal hydroxides For example, sodium hydroxide and potassium hydroxide are used.

When carrying out the process (Bα) according to the invention, the reaction temperature can vary within a relatively wide range. In general, the reaction is carried out at temperatures between -20 and +150 ° C, preferably between 0 and 100 ° C.

When carrying out process (Bα) according to the invention, the starting materials of the general formula (I-a) and the carbonyl halides of the general formula (III) are generally used in approximately equivalent amounts, respectively. However, it is also possible to use carbonyl halides in large amounts (up to 5 moles). Post-treatment is carried out in a conventional manner.

Process (Bβ) is characterized by reacting a compound of general formula (I-a) with a carboxylic anhydride of general formula (IV) in the presence of a diluent and optionally in the presence of an acid binder.

Suitable diluents for use in the process (Bβ) according to the invention are diluents which are preferably used when acyl halides are used. In addition, the carboxylic acid anhydride used in excess may also act as a diluent at the same time.

The acid binder optionally added to the process (Bβ) is also a preferred acid binder, preferably when acyl halides are used.

In the process (Bβ) according to the invention the reaction temperature can vary within a relatively wide range. In general, the reaction is carried out at temperatures between -20 and +150 ° C, preferably between 0 and 100 ° C.

When carrying out the process (Bβ) according to the invention, the starting materials of the general formula (I-a) and the carboxylic anhydrides of the general formula (IV) are generally used in approximately equivalent amounts, respectively. However, it is also possible to use carboxylic anhydride in large excess (5 mol or less). Post-treatment is carried out according to conventional methods.             

In general, the diluent and excess carboxylic anhydride and also the resulting carboxylic acid are removed by distillation or by washing with an organic solvent or water.

Method (C) is characterized in that a compound of formula (Ia) is reacted with chloroformic acid ester or chloroformic acid thiol ester of general formula (V) in the presence of a diluent and optionally in the presence of an acid binder do.

Suitable acid binders for use in process (C) according to the invention are all customary acid acceptors. These preferably include tertiary amines such as triethylamine, pyridine, DABCO, DBU, DBN, Wheinich base and N, N-dimethyl-aniline, further alkaline earth metal oxides such as magnesium oxide and Calcium oxide, alkali metal and alkaline earth metal carbonates such as sodium carbonate, potassium carbonate and calcium carbonate, and also alkali metal hydroxides such as sodium hydroxide and potassium hydroxide are used.

Suitable diluents for use in the process (C) according to the invention are all solvents which are inert to the chloroformic acid ester or chloroformic acid thiol ester. These are preferably hydrocarbons such as benzine, benzene, toluene, xylene and tetralin, further halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, ketones, Acetone and methylisopropyl ketones, ethers such as diethyl ether, tetrahydrofuran and dioxane, also carboxylic esters such as ethyl acetate, nitrile such as acetonitrile, and also steel Polar solvents such as dimethylformamide, dimethyl sulfoxide and sulfolane are used.             

When carrying out process (C) according to the invention, the reaction temperature can vary within a relatively wide range. In general, the reaction temperature is between -20 and +100 ° C, preferably between 0 and 50 ° C.

Process (C) according to the invention is generally carried out under atmospheric pressure.

When carrying out process (C) according to the invention, the starting materials of the general formula (I-a) and the suitable chloroformic acid esters or chloroformic acid thiol esters of the general formula (VII) are generally used in approximately equivalent amounts, respectively. However, it is also possible to use one component or another component in large amounts (up to 2 moles). Post-treatment is carried out according to conventional methods. In general, after the precipitated salt is removed, the diluent is removed under reduced pressure to concentrate the remaining reaction mixture.

Process (D) according to the invention is characterized by reacting a compound of formula (I-a) with a compound of formula (VI) in the presence of a diluent and, optionally, in the presence of an acid binder.

In the preparation process (D), about 1 mole of chloromonothioformic acid ester or chlorodithioformic acid ester of general formula (VI) per mole of starting material of general formula (Ia) is 0 to 120 ° C, preferably 20 to 60 The reaction is carried out at ℃.

Diluents which may optionally be added are all inert polar organic solvents such as ethers, amides, sulfones, sulfoxides, and halogenoalkanes.

Dimethyl sulfoxide, tetrahydrofuran, dimethylformamide, ethyl acetate or methylene chloride are preferably used.             

In a preferred embodiment, when the enolate salt of the compound of general formula (Ia) is prepared by addition of a strong deprotonating agent, for example sodium hydride or potassium t-butoxide, no additional acid binder can be added. have.

Suitable bases for use in method (D) are all conventional proton acceptors. As these, alkali metal hydrides, alkali metal alkoxides, alkali metal or alkaline earth metal carbonates or bicarbonates or nitrogen bases are used. Examples thereof include sodium hydride, sodium methoxide, sodium hydroxide, calcium hydroxide, potassium carbonate, sodium bicarbonate, triethylamine, dibenzylamine, diisopropylamine, pyridine, quinoline, diazabicyclooctane (DABCO), diazabicyclononene (DBN) and diazabicycloundecene (DBU).

The reaction may be carried out at atmospheric or elevated pressure, preferably at atmospheric pressure. Post-treatment is carried out according to conventional methods.

Process (E) according to the invention is characterized in that the compound of formula (Ia) is reacted with sulfonyl chloride of formula (VII), optionally in the presence of a diluent and optionally in the presence of an acid binder. .

In the preparation method (E), about 1 mole of sulfonyl chloride of the general formula (IX) is reacted at -20 to 150 ° C, preferably 0 to 70 ° C per mole of starting material of the general formula (I-a).

Process (E) is preferably carried out in the presence of a diluent.

Suitable diluents are all inert polar organic solvents such as ethers, amides, ketones, carboxylic acid esters, nitriles, sulfones, sulfoxides or halogenated hydrocarbons such as methylene chloride.

Dimethyl sulfoxide, tetrahydrofuran, dimethylformamide, ethyl acetate, methylene chloride are preferably used.

In a preferred embodiment, when the enolate salt of compound (I-a) is prepared by addition of a strong deprotonating agent (eg sodium hydride or potassium t-butoxide), further acid binders may not be added.

When using acid binders, customary inorganic or organic bases are suitable, which may, for example, mention sodium hydroxide, sodium carbonate, potassium carbonate, pyridine and triethylamine.

The reaction may be carried out at atmospheric or elevated pressure, preferably at atmospheric pressure. Post-treatment is carried out according to conventional methods.

Process (F) according to the invention is characterized by reacting a compound of general formula (I-a) with a phosphorus compound of general formula (VIII), optionally in the presence of a diluent and optionally in the presence of an acid binder.

In the preparation method (F), 1 to 2 moles, preferably 1 to 1.3 moles of the phosphorus compound of the general formula (VIII) per mole of the compound of the general formula (Ia) are -40 to 150 캜, preferably -10 to Reaction at a temperature between 110 ° C. affords a compound of formula (Ie).

Process (F) is preferably carried out in the presence of a diluent.

Suitable diluents are all inert polar organic solvents such as ethers, carboxylic acid esters, halogenated hydrocarbons, ketones, amides, nitriles, sulfones, sulfoxides and the like.

Acetonitrile, dimethyl sulfoxide, tetrahydrofuran, dimethylformamide or methylene chloride are preferably used.

Acid binders, which are optionally added, are conventional inorganic or organic bases such as hydroxides, carbonates or amines, which may include, for example, sodium hydroxide, sodium carbonate, potassium carbonate, pyridine and triethylamine.

The reaction may be carried out at atmospheric or elevated pressure, preferably at atmospheric pressure. Post-treatment is carried out according to conventional methods of organic chemistry. The final product is preferably purified by crystallization, chromatographic purification or so-called "incipient distillation", ie by removing the volatile components under reduced pressure.

Process (G) is characterized by reacting a compound of formula (I-a) with a metal hydroxide or metal alkoxide of formula (IX), or an amine of formula (X), optionally in the presence of a diluent.

Preferred diluents for process (G) according to the invention are ethers such as tetrahydrofuran, dioxane, diethyl ether, or alcohols such as methanol, ethanol, isopropanol, and also water. Process (G) according to the invention is generally carried out under atmospheric pressure. The reaction temperature is generally between -20 and 100 ° C, preferably between 0 and 50 ° C.

Process (H) according to the invention reacts a compound of formula (Ia) with a compound of formula (XI) in the presence of a (Hα) optionally a diluent and optionally a catalyst, or ( Hβ) is characterized in that it reacts with a compound of formula (XII), optionally in the presence of a diluent and optionally in the presence of an acid binder.

In the production process (Hα), about 1 mole of isocyanate of general formula (XI) is reacted at a temperature between 0 and 100 ° C, preferably between 20 and 50 ° C, per mole of starting material of general formula (I-a).

Method (Hα) is preferably carried out in the presence of a diluent.

Suitable diluents are all inert organic solvents, for example aromatic hydrocarbons, halogenated hydrocarbons, ethers, amides, nitriles, sulfones or sulfoxides.

In some cases, a catalyst may be added to promote the reaction. A catalyst that can be used very advantageously is an organotin compound, for example dibutyltin dilaurate.

The reaction is preferably carried out at atmospheric pressure.

In the preparation process (Hβ), about 1 mole of carbamoyl chloride of general formula (XIII) per 1 mole of starting material of general formula (I-a) is reacted at a temperature of 0 to 150 ° C, preferably 20 to 70 ° C.

Diluents which may optionally be added are all inert polar organic solvents, for example ethers, carboxylic acid esters, nitriles, ketones, amides, sulfones, sulfoxides or halogenated hydrocarbons.

Preference is given to using dimethyl sulfoxide, tetrahydrofuran, dimethylformamide or methylene chloride.

In a preferred embodiment, when the enolate salt of the compound of formula (Ia) is prepared by addition of a strong deprotonating agent (e.g. sodium hydride or potassium t-butoxide), no additional acid binder is added. Can be.

When using acid binders, customary inorganic or organic bases are suitable, which may be mentioned by way of example sodium hydroxide, sodium carbonate, potassium carbonate, triethylamine or pyridine.

The reaction may be carried out at atmospheric or elevated pressure, preferably at atmospheric pressure. Post-treatment is carried out according to conventional methods.

The active compounds are suitable for controlling animal pests, in particular arthropods and nematodes, in particular insects and arachnids, encountered in the fields of agriculture, forestry, storage and protection and hygiene. They are active against moderately sensitive or resistant species and all or some stages of development. The pests mentioned above include:

Isopoda neck, for example Oniscus asellus , Armadillidium vulgare and Porcellio scaber .

Millipedes (Diplopoda) tree, for example Blast niul loose obtain Tula tooth (Blaniulus guttulatus).

The genus Chilopoda , for example Geophilus carpophagus and Scutigera spec .

From the order of Symphyla , for example Scutigerella immaculata .

Thysanura , for example Lepisma saccharina .

Collembola neck, for example Onychiurus armatus .

Orthoptera , for example Blatta orientalis , Periplaneta americana , Leucophaea maderae , Blattella germanica , Ah keta also scalpel Tea Syracuse (Acheta domesticus), talpa species grill (Gryllotalpa spp.), Roku star US Gras Trattoria US Gras Tori cucumber death (Locusta migratoria migratorioides), melanocyte platforms Ruth Depeche Lenti Alice (Melanoplus differentialis) and the rest Stowe Sergio Cagregaria ( Schistocerca gregaria ).

Dermaptera , for example Forficula auricularia .

Termite Isoptera , for example Reticulitermes spp .

Anoplura , for example Phylloxera vastatrix , Pemphigus spp ., Pediculus humanus corporis , Haematopinus spp . And Linognathus spp .

Mallophaga , for example Trichodectes spp . And Damalinea spp .

From the order of Thysanoptera , for example Frankliniella occidentalis , Hercinothrips femoralis , Thrips palmi and Thrips tabaci ).

From the order of Heteroptera , for example Eurygaster spp ., Dysdercus intermedius , Piesma quadrata , Cimex lectularius , Rodney Rhodnius prolixus and Triatoma spp .

Cicadas (Homoptera) tree, for example, waters right Death in Brassica (Aleurodes brassicae), bemi cyano other dedicate (Bemisia tabaci), the tree Valley right des bar Fora Rio room (Trialeurodes vaporariorum), Apis notice blood (Aphis gossypii), the breather Vico Rhine Brassica (Brevicoryne brassicae), the creep Tommy juice Leavis (Cryptomyzus ribis), Apis wave bar (Aphis fabae), Doral less breech (Doralis pomi), Erie O Soma Raney gerum (Eriosoma lanigerum), hyaluronic rope Teruel's Hyalopterus arundinis , Macrosiphum avenae , Myzus spp ., Phorodon humuli , Rhopalosiphum padi , Empoasca species spp .), Euscelis bilobatus , Nephotettix cincticeps , Lecanium corni , Saissetia oleae , Lao delfax str Leah Ruth (Laodelphax striatellus), Neela Parque Bata Lou Regensburg (Nilaparvata lugens), Oh sludge de Ella Augusta is T (Aonidiella aurantii), ah Speedy ohtuseu Hedera (Aspidiotus hederae), pseudo nose Syracuse species (Pseudococcus spp.) And programs Syla species ( Psylla spp .)

Lepidoptera , for example Pectinophora gossypiella , Bupalus piniarius , Cheimatobia brumata , Lithocolletis blancardella , Hyponomeuta padella , Plutella maculipennis , Malacosoma neustria , Euproctis chrysorrhoea , Lymantria spp . , the unit Kula matrix Tour Barry Ella (Bucculatrix thurberiella), Philo greatest seutiseu sheet mozzarella (Phyllocnistis citrella), Agrobacterium-Tees species (Agrotis spp.), six pediatric species (Euxoa spp.), Pell Tia species (Feltia spp.), Earias insulana , Heliothis spp ., Spodoptera exigua , Mamestra brassicae , Panolis flammea Panolis flammea ), Prodenia litura , Spodoptera spp ., Trichoplusia ni , Carpocapsa pomonella , Pieris spp . ), Chilo spp ., Pyrausta nubilalis , Ephestia kuehniella , Galleria mellonella , Tineola bisselliella , T. Tinea pellionella , Hofmannophila pseudospretella , Cacoecia podana , Capua reticulana , Choristoneura fumiferana ), Clysia ambiguella , Homona magnanima and Tortrix viridana .

Coleoptera (e.g., Anobium punctatum ), Rhizopertha dominica , Acanthoscelides obtectus , Hylotrupes bajulus , Agelastica alni , Leptinotarsa decemlineata , Phaedon cochleariae , Diabrotica spp ., P. silicodes chrysepala ( Psylliodes chrysocephala ), Epilachna varivestis , Atomaria spp ., Oryzaephilus surinamensis , Anthonomus spp ., Cytophilus species (Sitophilus spp.), cut out ot kusu sulka tooth (Otiorrhynchus sulcatus), poly Cosmo test sorbitan di Douce (Cosmopolites sordidus), establish Torin kusu know mm's (Ceuthorrhynchus assimilis), hipe Force Galactica (Hypera postica), no scalpel test species (Dermestes spp.), Tree logo Dumaguete species (Trogoderma spp.), No trail pandanus species (Anthrenus spp.), Oh ridden pandanus species (Attagenus spp.), Rick tooth kind ( Lyctus spp .), Meligethes aeneus , Ptinus spp ., Niptus hololeucus , Gibbium psylloides , Tribolium species ( Tribolium spp .), Tenebrio molitor , Agriotes spp ., Conoderus spp ., Melolontha melolontha , Amphimalon soltialis ( Amphimallon solstitialis ) and Costelytra zealandica .

Hymenopera species, for example Diprion spp ., Hoplocampa spp ., Lasius spp ., Monomorium pharaonis and Vespa species Vespa spp .).

Diptera , for example Aedes spp ., Anopheles spp ., Culex spp ., Drosophila melanogaster , Musca species. Musca spp .), Fannia spp ., Calliphora erythrocephala , Lucilia spp ., Chrysomyia spp ., Cuterebra spp . , Gastrophilus spp ., Hypobosca spp ., Liriomyza spp ., Stomoxys spp ., Oestrus spp ., Hypoderma spp ., Tabanus spp ., Tannia spp ., Bibio hortulanus , Oscinella frit , Phorbia spp. ), Pegomyia hyoscyami , Ceratitis capitata , and Dactus oleea (.) Dacus oleae ) and Tipula paludosa .

From the order of Siphonaptera , for example Xenopsylla cheopis and Ceratophyllus spp .

Arachnida , for example Scorpio maurus and Latrodectus mactans .

Mite ( Acarina ), for example, Acarus siro , Argas spp ., Ornithodoros spp ., Dermanyssus gallinae , Eriopis libis ( Eriophyes ribis ), Phyllocoptruta oleivora , Boophilus spp ., Rhipicephalus spp ., Amblyomma spp ., Hyalomma spp. ., Ixodes spp ., Psoroptes spp ., Chorioptes spp ., Sarcoptes spp ., Tarsonemus spp . ), Bryobia praetiosa , Panonychus spp . And Tetranychus spp .

The active compounds according to the invention have very potent insecticidal and acaricide activity after leaf and soil application.

They are especially useful for insects that are harmful to plants, such as, for example, mustard beetle (Pedon cocleariae) larvae, cicada larvae (nepotetics cactifs) larvae and peach or aphids (Misso Pacifica) larvae. Can be used successfully.

The active compounds according to the invention can also be used as deciduous, drying, stem-killer and especially weed-removing agents. The term "weeds" means, in the broadest sense, all plants that grow in unwanted places. Whether the substance according to the invention acts as a total or selective herbicide depends essentially on the amount used.

The dose of the active compound according to the invention necessary for controlling weeds is from 0.001 to 10 kg / dl, preferably from 0.005 to 5 kg / dl.

The active compounds according to the invention can be used, for example, in connection with the following plants:

The ssangjayeop weeds in the To: Sina piece (Sinapis), Les pidyum (Lepidium), gallium (Galium), Stella Ria (Stellaria), Mart Rica Ria (Matricaria), Ante Miss (Anthemis), ground cattle (Galinsoga), Kane Chenopodium , Urtica , Senecio , Amaranthus , Portulaca , Xanthium , Convolvulus , Ipomoea , Polygonum (Polygonum), access Vania (Sesbania), Ambrosia (Ambrosia), unsealing syum (Cirsium), carboxylic Douce (Carduus), hand kusu (Sonchus), Solar num (Solanum), roripa (Rorippa), in Tallahassee (Rotala ), Lin der California (Lindernia), La hate (Lamium), Veronica (Veronica), Abu epothilone (Abutilon), the Mex (Emex), Datura (Datura), viola (viola), Gale option system (Galeopsis), Papaver , Centaurea , Trifolium , Ranunculus and Taraxacu m ).

S to the genus ssangjayeop crops: Notice europium (Gossypium), glycidyl cine (Glycine), Beta (Beta), Dow kusu (Daucus), Pace come loose (Phaseolus), pisum (Pisum), Solar num (Solanum), rinum (Linum ), Ipomoea , Vicia , Nicotiana , Lycopersicon , Arachis , Brassica , Lactuca , Cucumis ) And Cucurbita .

Monocot weeds in the genus : Echinochloa , Setaria , Panicum , Digitaria , Phleum , Poa , Festuca , Eleusin , Brachiaria , Lolium , Bromus , Avena , Cyperus , Sorghum , Agropyron , Sino Cynodon , Monochoria , Fimbristylis , Sagittaria , Eleocharis , Scirpus , Paspalum , Ischaemum ), Spanish no nuclease (Sphenoclea), daktil lock'll help (Dactyloctenium), Agrobacterium seutiseu (Agrostis), allo page kuruseu (Alopecurus) and ahpera (Apera).

S to the genus monocot crops: Duck Party (Oryza), ZE (Zea), tree tikum (Triticum), Johor deum (Hordeum), ABE or (Avena), three-Calais (Secale), sorbitol gum (Sorghum), Trapani Qom ( Panicum), Saccharomyces Room (Saccharum), Ananas (Ananas), aspartate Goose (Asparagus) and Allium (Allium).

However, the use of the active compounds according to the invention is not limited at all in the above and extends to other plants in the same way.

The compounds of the invention are suitable for the overall control of weeds, depending on concentration, for example on industrial areas and railways, and on sidewalks and plazas with or without trees. Similarly, the compounds of the present invention are for example planted plants, ornamental water plantations, orchards, vineyards, citrus fields, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, palm plantations, cocoa plantations, soft fruit plantations and It can be used to control weeds in perennial crops growing on hop fields, decorative and sports grasses and pastures, and to selectively control weeds in annual crops.

The active compounds according to the invention are suitable for the selective control of monocotyledonous weeds in dicotyledonous crops by both pre- and post-germination methods. They can be used very successfully, for example, in combating harmful grasses from cotton or beets.

The active compounds according to the invention are very fine in solutions, emulsions, hydrating powders, suspensions, powders, powders, pastes, soluble powders, granules, suspension-emulsion concentrates, natural and synthetic substances impregnated with the active compounds, and polymers. It may be converted into a conventional formulation such as a capsule.

These formulations are prepared by known methods, for example by mixing the active compounds with extenders, ie liquid solvents and / or solid carriers, optionally using surfactants, ie emulsifiers and / or dispersants and / or foam-forming agents. .

If the extender used is water, for example organic solvents can also be used as auxiliary solvents. Suitable liquid solvents are mainly aromatic compounds such as xylene, toluene or alkylnaphthalene, chlorinated aromatic and chlorinated aliphatic hydrocarbons such as chlorobenzene, chloroethylene or methylene chloride, cyclohexane or paraffins, for example petroleum fractions, mineral oils and vegetable oils. Alcohols such as aliphatic hydrocarbons, butanol or glycol and ethers and esters thereof, water such as ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, dimethylformamide and dimethyl sulfoxide as well as water .

Suitable solid carriers are, for example, ammonium salts and ground natural minerals such as kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground powders such as highly dispersed silica, alumina and silicates. It is a synthetic mineral. Suitable granular solid carriers are, for example, pulverized and classified natural rocks such as calcite, marble, pumice, calcite and dolomite, and synthetic granules of inorganic and organic powders, and sawdust, coconut husks, corncobs and tobacco stems. Granules of organic matter. Suitable emulsifiers and / or foam-forming agents are for example nonionic and anionic emulsifiers, for example polyoxyethylene fatty alcohol ethers such as polyoxyethylene fatty acid esters, alkylaryl polyglycol ethers, alkylsulfonates, alkylsulfates, Arylsulfonates and proteolytic products. Suitable dispersants are, for example, lignin-sulphite waste liquors and methylcellulose.

Adhesives such as carboxymethylcellulose, gum arabic, polyvinyl alcohol and powders such as polyvinyl acetate, natural and synthetic polymers in the form of granules or latex, and natural phospholipids such as cephalin and lecithin, and synthetic phospholipids may be used in the formulation. Can be. As other additives, mineral oil and vegetable oil may be used.

Colorants such as inorganic pigments such as iron oxide, titanium oxide and prussian blue, and organic dyes such as alizarin dyes, azo dyes and metal phthalocyanine dyes and salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc Micronutrients may also be used.

The formulations generally contain 0.1 to 95% by weight, preferably 0.5 to 90% by weight of the active compound and also preferably extenders and / or surfactants.

The active compounds according to the invention are prepared from commercially available formulations and mixtures of these with other active compounds such as insecticides, attractants, fungicides, acaricides, nematicides, fungicides, growth-modulating substances or herbicides. May exist in the form of use. Pesticides include, for example, phosphate esters, carbamates, carboxylic acid esters, chlorinated hydrocarbons, phenylurea, materials produced by microorganisms, and the like.

Examples of particularly advantageous mixing partners are as follows:

Fungicides:

2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyrimidine; 2 ', 6'-dibromo-2-methyl-4'-trifluoromethoxy-4'-trifluoro-methyl-1,3-thiazole-5-carboxanilide; 2,6-dichloro-N- (4-trifluoromethylbenzyl) -benzamide; (E) -2-methoxyimino-N-methyl-2- (2-phenoxyphenyl) -acetamide; 8-hydroxyquinoline sulfate; Methyl (E) -2- {2- [6- (2-cyanophenoxy) -pyrimidin-4-yloxy] -phenyl} -3-methoxyacrylate; Methyl (E) -methoximino [alpha- (o-tolyloxy) -o-tolyl] acetate; 2-phenylphenol (OPP),

Aldimorph, Ampropyl Force, Anilazine, Azaconazole,

Benalacyl, benodanil, benomil, vinapacryl, biphenyl, biteranol, blasticidin-S, bromuconazole, burimate, butiobate,

Calcium polysulfide, captapol, captan, carbendazim, carboxycin, quinomethionate, chloroneb, chloropicrine, chlorothalonil, clozolinate, cupraneb, cymoxanyl, cyproconazole, cyprofuram,

Dichlorophene, diclobutrazole, diclofluanide, diclomezin, dichloran, dietofencarb, difenokazole, dimethymolol, dimethomorph, diconazole, dinocap, diphenylamine, Depyrithione, ditalimfoss, dithianon, dodine, drazoxolone,             

Edifene Force, Epoxyconazole, Ethirimol, Etridiazole,

Phenarimol, fenbuconazole, fenfuram, phenytropane, fenpiclonil, phenpropidine, fenpropormph, fentin acetate, fentin hydroxide, ferbam, perimzone, fluazinam, fludioxonyl, Fluoromides, fluquinonezol, flusilazole, flusulfamid, flutolanil, flutriafol, polpet, pocetyl-aluminum, phthalide, fuberidazole, furlaxyl, purmecyclox,

Guazatin,

Hexachlorobenzene, hexaconazole, hymexazole,

Imazalil, imibenconazole, iminottadine, ifprobenfos (IBP), iprodione, isoprothiolane,

Kasugamycin, copper preparations such as copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxide, auxin-copper and Bordeaux mixtures, mancopers, mancozebs, manebs, mepanipyrim, Mepronyl, metallaxyl, metconazole, metasulfocarb, metfuroxam, metiram, metsulfobox, michaelrobutanyl,

Nickel dimethyldithiocarbamate, nitrotal-isopropyl, noarimol,

Opuras, Oxadixyl, Oxamocarb, Oxycarboxine,

Pepurazoate, Fenconazole, Penicuron, Phosphofen, Phthalide, Fimaricin, Pipeline, Polycarbamate, Polyoxin, Provenazole, Prochloraz, Procimidone, Propamocarb, Propico Nazol, propineb, pyrazophos, pyriphenox, pyrimethanyl, pyroquilon,             

Quintogen (PCNB),

Sulfur and sulfur preparations,

Tebuconazole, Teclophthalam, Tecnazene, Tetraconazole, Tiabendazole, Tiothiophene, Thiophanate-methyl, Thiram, Tollclofos-methyl, Tolylufluoride, Triadimefon, Triadimenol, Triazosides, triclamides, tricyclazoles, tridemorphs, triflumisols, tripolins, triticazoles,

Validamycin A, vinclozoline,

Genev, sir.

disinfectant:

Bronopol, dichlorophene, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octylinone, furancarboxylic acid, oxytetracycline, probenazole, streptomycin, teclophthalam, copper sulfate and other copper agents.

Pesticides / Acaricides / Nematicides:

Abamectin, AC 303 630, Acetate, Acrinatrin, Alanicab, Aldicarb, Alphamethrin, Amitraz, Avermectin, AZ 60541, Azadirachtin, Ajinfoss A, Ajinfoss M, Azo Cyclotin,

Bacillus thuringiensis, bendiocarb, benfuracarb, bensultap, beta-cyfluthrin, bifenthrin, BPMC, brofenprox, bromophos A, bufencarb, buprofezin, buttocaxin, butylpyri Daben,

Cadusafos, cabaril, cabofuran, cabofennotion, cabosulphan, katop, CGA 157 419, CGA 184 699, cloetocarb, chlorethoxy force, chlorfenbinfos, chlorfluazuron, chlormephos, chlor Pyriphos, Chlorpyriphos M, Cis-Resmethrin, Closightrin, Clofenthezin, Cyanophos, Cycloprotrin, Cyfluthrin, Cyhalothrin, Cyhexatin, Cypermethrin, Cyromazine,

Deltamethrin, Demethone-M, Demethone-S, Demethone-S-methyl, Diapentiouron, Diazinon, Diclopention, Dichlorbos, Diclifoss, Dicrotophos, Diethion, Difluben Juron, Dimethoate, Dimethylbinfos, Dioxation, Disulfotone,

Edifene force, emamectin, esfen valerate, thiophencarb, ethion, etofenprox, etoprofos, erythropose,

Phenamifos, phenaquinone, fenbutatin oxide, phenythrothione, phenobcarb, phenothiocarb, phenoxycarb, phenpropatrine, fenpyrad, fenpyroximate, pention, fenvalrate, fipro Neil, Fluazinam, Flucycloxonon, Flucytinate, Flufenoxuron, Flufenprox, Fluvalinate, Phonophos, Formotion, Phosthiazate, Pufenfenrox, Furateocarb,

HCH, heptenophos, hexaflumuron, hexthiaxans,

Imidacloprid, ifprobenfoss, isazofoss, isofenfoss, isoprocarb, isoxation, ivermectin,

Lambda-cyhalothrin, lufenuron,

Malathion, Mecarbam, Mevinforce, Mesulfenphos, Metaldehyde, Methacryfoss, Metamidophos, Metidathione, Methiocarb, Methomil, Mettolcarb, Milvemectin, Monochrome topos, Moxidexine,

Nalred, NC 184, NI 25, nitenpyram,

Ometoate, oxamyl, oxydemethone M, oxydepropos,

Parathion A, Parathion M, Permethrin, Pentoate, Forate, Posalon, Phosmet, Phosphomidone, Bombardment, Pyrimicarb, Pyrimiphos M, Pyrimiphos A, Propenophos, Promecab, Propa Phos, propoxur, prothiophos, protoate, pymetrozine, pyraclophos, pyridapention, pyresmethrin, pyrethrum, pyridaben, pyrimidipene, pyripropoxyphene,

Quinal Force,

RH 5992,

Salitione, cebufoss, silafluorene, sulfotep, sulfpropos,

Tebufenozide, Tebufenpyrad, Tebupyrimifos, Teflubenzuron, Tefluthrin, Temefoss, Terbam, Terbufoss, Tetrachlorbinfos, Thiaphenox, Thiodicarb, Thiophanox, Thiomethone, thiazineazine, turingiencin, tralomethrin, triarathene, triazofoss, triazuron, trichlorphone, triflumuron, trimetacarb,

Vamidothione, XMC, xylylcarb, YI 5301/5302, zetamethrin.

Herbicides :

Anilides such as, for example, diflufenican and propanyl; Arylcarboxylic acids such as, for example, dichloropicolinic acid, dicamba and picloram; Aryloxyalkanoic acids such as, for example, 2,4 D, 2,4 DB, 2,4 DP, fluoxypyr, MCPA, MCPP, and triclopyr; Aryloxy-phenoxy-alkanoic acid esters such as, for example, diclopov-methyl, phenoxaprop-ethyl, fluazifop-butyl, halooxypop-methyl, and quinacofop-ethyl; Azinones such as, for example, chloridazone and norflurazon; Carbamate, such as chlorprofam, desmedapem, penmedipam, and profam; Chloroacetanilides such as, for example, alachlor, acetochlor, butachlor, metazachlor, metolachlor, pretilachlor, and propachlor; Dinitroanilines such as, for example, oryzaline, pendimethalin and trituralin; Diphenyl ethers such as, for example, asifluorophene, biphenox, fluoroglycopene, pomesafen, halosafen, lactofen and oxyfluorfen; Ureas such as, for example, chlortoluron, diuron, fluoromethuron, isoproturon, linuron and metabenzthiazuron; Hydroxylamines such as, for example, alkoxydim, cletodim, cycloxydim, cetoxydim and trakoxydim; Imidazolinones such as for example imazetapyr, imazamethabenz, imazapyr and imazaquin; Nitriles such as, for example, bromoxynil, diclobenyl and oxynyl; Oxyacetamides such as for example mefenacet; For example amidosulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorsulfone, cynosulfuron, metsulfuron-methyl, nicosulfuron, primisulfuron, pyrazosulfuron-ethyl, thifensulfuron-methyl Sulfonylureas such as triasulfuron and tribenuron-methyl; Thiocarbamates, such as, for example, butyrate, cycloate, di-acrylate, EPTC, esprocarb, molinate, prosulfocarb, thiobencarb and tri-alate; Triazines such as, for example, atrazine, cyanazine, simazine, cymetrin, terbutryn and terbutylazine; Triazinones such as, for example, hexazinone, metamitrone, and metrizine; For example aminotriazole, benfuresate, bentazone, synmethylin, clomazone, clopyralide, dipfencuart, dithiopyr, etofumesate, fluorochloridone, glufosinate, glyphosate And others such as isoxaben, pyridate, quinclolac, quinmerak, sulfosate and tridiphane.

The active compounds according to the invention can also be present in admixture with synergists in their commercially available formulations and in the use forms prepared from these formulations. Synergists are compounds that increase the action of the active compound without the need for the synergist added itself to be activated.

The active compound content of the use forms prepared from commercially available formulations can vary within wide limits. The concentration of the active compound of the use form is 0.0000001 to 95% by weight, preferably 0.0001 to 1% by weight.

The compound is used in a conventional manner suitable for the use form.

When used in hygienic pests and stored pests, the active compounds according to the invention exhibit excellent residual activity against wood and clay and excellent stability against alkalis on lime substrates.

The active compounds according to the invention are not only plant and sanitary pests, but also stored stock pests, as well as animal parasites (in vitro parasites) in the field of veterinary medicine, for example, hard mites, mollusks, mites, scabies mites, harvest mites, flies Vampire), parasitic fly larvae, teeth, hairy teeth, algae teeth and fleas. These parasites include:

Anoplurida , for example Haematopinus spp ., Linognathus spp ., Pediculus spp ., Pthirus spp ., Sole Novotes spp .

Hairs (Mallophagida) neck and arm assembly Serena (Amblycerina) and yiseukeu furnace Serena (Ischnocerina) suborder, such as tree Agate phone species (Trimenopon spp.), Agate phone species (Menopon spp.), Trinoton spp (teurino tone species. ), Bovicola spp ., Werneckiella spp ., Lepikentron spp ., Damalina spp ., Trichodectes spp ., Felicola spp .

Diptera and Nematocerina and Brachycerina subfamily, for example Aedes spp ., Anopheles spp ., Culex spp ., simul Solarium species (Simulium spp.), Yushi water Solarium species (Eusimulium spp.), play bottoming mousse species (Phlebotomus spp.), Lucho Mia species (Lutzomyia spp.), Cooley Koh des species (Culicoides spp.), chestnut Thorpe Crysops spp ., Hybomitra spp ., Atylotus spp ., Tabanus spp ., Haematopota spp ., Filippomia spp . Philipomyia spp .), Braula spp ., Musca spp ., Hydrotaea spp ., Stomoxys spp ., Haematobia spp . , Morelia species (Morellia spp.), plates Chania species (Fannia spp.), Gloucestershire Sinai species (Glossina spp.), Carly Fora species (Calliphora spp.), rusilriah species (Lucili a spp .), Chrysomyia spp ., Wohlfartia spp ., Sarcophaga spp ., Oestrus spp ., Hypoderma spp . ), Gasterophilus spp ., Hyppobosca spp ., Lipoptena spp ., Melophagus spp .

Siphonaptera species, for example Pulex spp ., Ctenocephalides spp ., Xenopsylla spp ., Ceratophyllus spp .

From the order of Heteroptera , for example Cimex spp ., Triatoma spp ., Rhodnius spp ., Panstrongylus spp .

Blattarida , for example Blatta orientalis , Periplaneta americana , Blatta germanica and Supella spp .

Mites; (. Ornithodorus spp) (Acarina Acarida) subclass and meta-and meso stigmasterol other (Meta and Mesostigmata) tree, for example, are the gas species (. Argas spp), ornithine Todo loose species, Ota Flavian species Otabius (spp .), ikso des species (Ixodes spp.), cancer Bulletin Mama species (Amblyomma spp.), bupil loose species (Boophilus spp.), der town centaur species (Dermancentor spp.), under the town killed less species (Haemaphysalis spp. ), Hyalomma spp ., Rhipicephalus spp ., Dermanyssus spp ., Raillietia spp ., Pneumonyssus spp . , Sternostoma spp . And Varroa spp .

Actinedida ( Prostigmata ) and Acaridida ( Astigmata ) necks, for example Acarapis spp ., Cheyletiella spp . ), Ornithocheyletia spp ., Myobia spp ., Psorergates spp ., Demodex spp ., Trombicula spp . , Listrophorus spp ., Acarus spp ., Tyrophagus spp ., Caloglyphus spp ., Hypodectes spp . , Pterolichus spp ., Psoroptes spp ., Chorioptes spp ., Otodectes spp ., Sarcoptes spp . dress species in Noto (Notoedres spp.), shown immense Cope test species (Knemidocoptes spp.), Citrus di test species (Cytodites spp.) and Minoh off test species (Laminosioptes spp.).

The active compounds of formula (I) according to the invention are also useful for agriculturally produced livestock such as cattle, sheep, goats, horses, pigs, donkeys, camels, buffaloes, rabbits, chickens, turkeys, ducks, geese and bees, and It is suitable for controlling pets such as arthropods that invade dogs, cats, birds in fish cages and fish tanks, and also so-called laboratory animals such as hamsters, guinea pigs, rats and mice. Arthropod control reduces mortality and yield reduction (e.g. in the production of meat, milk, wool, leather, eggs, honey, etc.), making the use of the active compounds according to the invention more economical and convenient. Animal care is possible.

In the field of veterinary medicine, the active compounds according to the invention are administered parenterally, for example by enteral administration in the form of tablets, capsules, beverages, potions, granules, pastes, cyclic agents, methods via drugs and suppositories, eg For example by injection (intramuscular, subcutaneous, intravenous and intraperitoneal, etc.), in the form of insertions, by intranasal administration, for example in the form of dipping or dipping, spraying, swelling and dropping, washing and misting And in the form of shaped articles containing the active compounds, for example in the form of necklaces, ear marks, tail marks, leg bands, bridles or indicators, in a known manner by transdermal use.

When used in livestock, poultry, pets, etc., the active compounds of general formula (I) are prepared as preparations (e.g. powders, emulsions, flowables) containing from 1 to 80% by weight of active compound. It may be used directly or diluted 100 to 10,000 times, or may be used in the form of a chemical bath.

It has also been found that the compounds of the general formula (I) according to the present invention exhibit potent insecticidal action against insects that destroy industrial materials.

The following insects may be mentioned as preferred examples, but are not limited to these:

Beetles , for example, Hylotrupes bajulus , Chlorophorus pilosis , Anobium punctatum , Xestobium rufovillosum , Ptilinus pecticornis , Dendrobium pertinex , Ernobius mollis , Priobium carpini , Lyctus brunneus , Rick Lyctus africanus , Lyctus planicollis , Lyctus linearis , Lyctus pubescens , Trogoxylon aequale , Mintes Minthes rugicollis , Zyleborus spp ., Tryptodendron spp ., Apate monachus , Bostrychus capucins , Heterobostrychus brunnes , Synoxylon spp . And Dinoderus minutus .

Hymenopterans , for example Sirex jubencus , Urocerus gigas , Urocerus gigas taignus , Uroserus augur ( Urocerus augur ).

Termites , for example, Kalotermes flavicollis , Cryptotermes brevis , Heterotermes indicola , Reticulitermes flavipes , Reticulitermes santonensis , Reticulitermes lucifugus , Mastotermes darwiniensis , Zootermopsis nevadensis and Coff Coptotermes formosanus

Bristletails , for example Lepisma saccharina

Industrial materials in the context of the present invention are understood in the sense of non-living materials, for example plastics, adhesives, sizes, papers and cards, leather, wood and processed wood products, and lacquers and paints.

Materials that must be very particularly protected against pest infestation are wood and processed wood products.

Wood and processed wood products which may be protected by the preparations or mixtures containing them according to the invention are for example construction wood, wood beams, railway sleepers, bridge components, thighs, wooden vehicles, boxes, It is understood to mean wood products which are very commonly used in pallets, containers, telephone poles, wooden signs, windows and doors made of wood, plywood, chip boards, connectors, or building construction or building connections.

The active compounds can be used on their own in the form of concentrates or common conventional preparations, for example powders, granules, solutions, suspensions, emulsions or pastes.

The formulations mentioned are known per se, for example, the active compound may be at least one solvent or diluent, emulsifier, dispersant and / or binder or fixative, waterproofing agent, optionally desiccant and UV stabilizer and optionally It can be prepared by mixing with dyes and pigments and other processing aids.

Insecticidal compositions or concentrates used to protect wood and processed wood products therefrom contain active compounds according to the invention in concentrations of from 0.0001 to 95% by weight, in particular from 0.001 to 60% by weight.             

The amount of composition or concentrate used depends on the nature and frequency of the pest and the medium. Optimal use can be determined in each case by a series of tests. In general, however, it is sufficient to use from 0.0001 to 20% by weight of active compound, preferably from 0.001 to 10% by weight, based on the substances to be protected.

The solvents and / or diluents used are organic chemical solvents or solvent mixtures and / or low volatility oily or oily organic chemical solvents or solvent mixtures and / or polar organic chemical solvents or solvent mixtures and / or water, and emulsifiers and / or if appropriate Or humectant.

Preferably, an oily or oily solvent having an evaporation number of at least 35 and a flash point of at least 30 ° C, preferably at least 45 ° C, is used as the organic chemical solvent. Corresponding mineral oils or their aromatic fractions, or mixtures of mineral oil-containing solvents, preferably White spirit, petroleum and / or alkylbenzenes, are used as oily and oily solvents which are low volatility and water-insoluble.

Mineral oil having a boiling range of 170 to 220 ° C, white oil having a boiling range of 170 to 220 ° C, spindle oil having a boiling range of 250 to 350 ° C, petroleum or aromatic compound having a boiling range of 160 to 280 ° C, terebin ( terpentine) oil and the like are advantageously used.

In a preferred embodiment, liquid aliphatic hydrocarbons having a boiling range of 180 to 210 ° C. or high-boiling mixtures of aromatic and aliphatic hydrocarbons having a boiling range of 180 to 220 ° C. and / or spindle oil and / or monochloronaphthalene, preferably Α-monochloronaphthalene is used.

Low volatility organic oily or oily solvents having an evaporation index of at least 35 and a flash point of at least 30 ° C., preferably at least 45 ° C., wherein the solvent mixture also has a flash point of at least 35 and a flash point of at least 30 ° C., preferably at least 45 ° C. If the pesticide / fungicide mixture can be dissolved or emulsified in this solvent mixture, it may be partially replaced by an intermediate or high volatility organic chemical solvent.

According to a preferred embodiment, a portion of the organic chemical solvent or solvent mixture is replaced with an aliphatic polar organic chemical solvent or solvent mixture. For example, aliphatic organic chemical solvents having hydroxyl and / or ester and / or ether groups such as glycol ethers, esters and the like are preferably used.

The organic chemical binders used within the scope of the present invention are known per se and are synthetic resins and / or combined dry oils, in particular acrylics, which can be diluted with water and / or dissolved, dispersed or emulsified in the organic solvent used. Rate resins, vinyl resins such as polyvinyl acetate, polyester resins, polycondensation or polyaddition resins, polyurethane resins, alkyd resins or modified alkyd resins, phenolic resins, hydrocarbon resins such as indene / coumar Binders consisting of or comprising coumarone resins, silicone resins, dry vegetable oils and / or dry oils and / or natural and / or synthetic resins and dried by physical means.

Synthetic resins used as binders can be used in the form of emulsions, dispersions or solutions. Bitumen or bitumen materials up to 10% by weight may also be used as binder. In addition, dyes, pigments, waterproofing agents, odor masking agents and inhibitors or corrosion inhibitors known per se may further be used.

Preferably, the composition or concentrate according to the invention preferably contains at least one alkyd resin or modified alkyd resin and / or dry vegetable oil as an organic chemical binder. Alkyd resins having an oil content of at least 45% by weight and preferably from 50 to 68% by weight are preferably used according to the invention.

All or part of the above mentioned binders may be replaced with fixatives (mixtures) or plasticizers (mixtures). These additives are used to prevent evaporation and crystallization or precipitation of the active compounds. They preferably replace 0.01 to 30% of the binder (based on 100% of the binder used).

Plasticizers include phthalic acid esters such as dibutyl, dioctyl or benzyl butyl phthalate, phosphoric acid esters such as tributyl phosphate, adipic acid esters such as di- (2-ethylhexyl) adipate, From the chemical groups of stearates such as butyl stearate or amyl stearate, oleates such as butyl oleate, glycerol ether or higher molecular weight glycol ethers, glycerol esters and p-toluenesulfonic acid esters Induced.

The fixative is chemically based on polyvinyl alkyl ethers such as polyvinyl methyl ether, or ketones such as benzophenone or ethylene benzophenone.

If desired, water mixed with one or more of the aforementioned organic chemical solvents or diluents, emulsifiers and dispersants is also possible as a solvent or diluent.             

Wood is particularly effectively preserved by large scale industrial injection methods, for example by vacuum, double vacuum or compression treatment.

If desired, the ready-to-use composition may also contain other pesticides and, if appropriate, also one or more fungicides.

Possible further mixing partners are preferably the insecticides and fungicides mentioned in WO 94/29 268. The compounds mentioned in this document are clearly components of the present application.

Particularly preferred mixing partners are insecticides such as chlorpyriphos, bombardment, silafluorine, alphamethrin, cyfluthrin, cypermethrin, deltamethrin, permethrin, imidacloprid, NI-25, flufenoxuron, Hexaflumuron and triflumuron, and fungicides, for example epoxyconazole, hexaconazole, azaconazole, propiconazole, tebuconazole, cyproconazole, metconazole, imazaryl, dichlor Fluanide, tolylufluoride, 3-iodo-2-propynylbutylcarbamate, N-octyl-isothiazolin-3-one and 4,5-dichloro-N-octylisothiazolin-3-one to be.

Examples of preparation and use of the active compounds according to the invention can be seen from the following examples.             

Example

Example (I-a-1)

At reflux temperature, 24.8 g of the compound of Example (II-2) in 150 ml of anhydrous toluene are added dropwise to 18.4 g (0.16 mol) of potassium t-butoxide in 63 ml of anhydrous tetrahydrofuran (THF) and the mixture is added for 1.5 hours. Stirred at reflux. 240 ml of water were added and the phases were separated and then the toluene phase was extracted with water. The combined aqueous phases were washed with toluene and acidified with about 26 mL of concentrated hydrochloric acid at 10-20 ° C. The precipitated solid was washed by suction filtration and dried. For purification, the product was stirred in a mixture of methyl t-butyl ether (MTB ether) and n-hexane.

Yield: 15.6 g (69% of theory), Melting point:> 220 ° C.

Similarly to the above process and / or according to the general preparation, compounds of the general formula (I-a) are obtained:             

TABLE 2

Example (I-b-1)

2.52 mL (18 mmol) of triethylamine was added to 3.62 g of the compound of Example (I-a-1) in 70 mL of anhydrous methylene chloride. At 0-10 ° C., 1.9 ml (18 mmol) of isobutyryl chloride in 5 ml of anhydrous methylene chloride was added to the mixture and stirring was continued until the reaction was completed at room temperature. Thereafter, the mixture was washed twice with 50 ml of 0.5N NaOH each time, dried and concentrated. The residue was recrystallized from MTB ether / n-hexane.

Yield: 1.6 g (35% of theory), Melting point: 209 ° C.

Similarly to the above process and / or according to the general preparation, compounds of the general formula (I-b) are obtained:             

TABLE 3

1) ¹ H-NMR (200 MHz, CDCl ₃ ): δ = 1.0-1.05 (4s, 6H, CH ( CH ₃ ) ₂ ), 2.25, 2.28 (25, 6H, Ar CH ₃ ).

Example (I-c-1)

At 0 to 10 ° C., 1.2 ml (12 mmol) of ethyl chloroformate in 5 ml of anhydrous methylene chloride, 1.7 ml (12 mmol) of triethylamine in 70 ml of anhydrous methylene chloride and 3.62 g of the compound of Example (Ia-1) Was added dropwise and the mixture was stirred at rt until the reaction was complete. The mixture was then washed twice with 50 ml of 0.5N NaOH each time, dried, concentrated and recrystallized with MTB ether / n-hexane.

Yield: 2.70 g (60% of theory), Melting point: 217 ° C.

Similarly to the above process and / or according to the general preparation, compounds of the general formula (I-c) are obtained:             

Table 4

Example (II-1)

At 30 to 40 ° C., 27.8 g of the compound of Example (XXIII-1) in 180 ml of methylene chloride were added dropwise to 45.4 g of concentrated sulfuric acid, and the mixture was stirred at 30 to 40 ° C. for 2 hours. Thereafter, 64 mL of anhydrous methanol was added dropwise, and the mixture was further stirred at 40 to 70 DEG C for 6 hours. The mixture was poured into 0.46 kg of ice and extracted with methylene chloride, then the organic phase was washed with aqueous NaHCO ₃ solution, then dried and concentrated. The residue was recrystallized from MTB ether / n-hexane.

Yield: 19.80 g (64% of theory), Melting point: 101 ° C.

Example (II-2)

At 0-10 ° C., 19.6 g of mesityleneacetyl chloride in 20 mL of dry THF are added dropwise to 30.8 mL (0.22 mole) of triethylamine and 20.98 g of the compound of Example (XIII-1) in 200 mL of dry THF, and the mixture is Stir at room temperature until the end of the reaction. The mixture was suction filtered, the filter cake was rinsed and the filtrate was concentrated. The residue was dissolved in methylene chloride and then washed with 200 mL 1N HCl, dried and concentrated. Silicagel column chromatography using 2/1 cyclohexane / ethyl acetate gave 24.0 g (72% of theory).

¹ H-NMR (200 MHz, CDCl ₃ ): δ = 1.12 (d, 3H, CH- CH ₃ ), 3.51 (α), 3.6 (β) (2s, 2H, CH ₂ , CONH, β / α, about 3: 1), 3.71, 3.75 (α / β) (2s, 3H, CO ₂ CH ₃ , (β / α 3: 1), 6.90 (α), 6.92 (β) (2s, 2H, ArH).

Similarly to the above process and / or according to the general preparation, compounds of the general formula (II) are obtained:             

Table 5

Example (XIII-1)

At 0-5 ° C., 73.2 mL (0.87 mole) thionyl chloride is added dropwise to 92.3 g of the compound of Example (XVI-1) in 870 mL of anhydrous methanol, and the mixture is stirred at about 0 ° C. for 30 minutes, then about Stir overnight at 40 ° C. After the mixture was filtered and the filtrate was concentrated, the residue was stirred with a small amount of MTB ether, then the mixture was suction filtered, the filter cake was rinsed and dried.

Yield: 87.0 g (86% of theory), Melting point:> 220 ° C.

Example (XVI-1)

130 g of NaOH in 2.5 L of water and 122.8 g of the compound of the following example were heated at 195 ° C. in an autoclave for 2 hours (the pressure rose to about 20 bar). The mixture is then concentrated to about one third of its volume, concentrated HCl is added at 0-10 ° C. until the pH is 5-6, the mixture is concentrated and the residue is boiled with methanol, The mixture was suction filtered and the filtrate was concentrated.

Yield: 92.3 g (86% of theory), Melting point:> 220 ° C.

Example Compounds of the Structural Formula

In an autoclave, a mixture containing 76 g of 3-methyl-tetrahydropyran-4-one, 71.9 g (1.468 mol) of sodium cyanide, 96 g (1 mol) of ammonium carbonate, 1.32 L of concentrated ammonia solution and 1.32 L of ethanol Was stirred at 120 ° C. for 3 hours, at which time the internal pressure rose to about 60 bar (2/3 of the desired reaction pressure was added before heating). The mixture was concentrated, dried over toluene, then boiled with methanol and suction filtered. The mother liquor was concentrated to 400 mL and the solid component was precipitated by addition of MTB ether followed by suction filtration. The mother liquor was concentrated. The residues were combined and boiled in ethanol, the mixture was suction filtered (A) and the filtrate was concentrated (B). (A) and (B) were combined.

Yield: 126.0 g (100% of theory).

Example (XXIII-1)

At 0 to 10 ° C., 21.6 g of mesitylene acetyl chloride in 20 mL of dry THF are added dropwise to 15.4 mL of triethylamine in 220 mL of dry THF and 15.6 g of the compound of Example (XXII-1), and the mixture is allowed to react at room temperature. Stir until finished. The mixture was stirred in 0.6 L of ice water and 0.2 L of 1N HCl, filtered off with suction, and the residue was dissolved in methylene chloride. After the solution was dried and concentrated, the residue was recrystallized from MTB ether / n-hexane.

Yield: 27.8 g (84% of theory), Melting point: 121 ° C.

Similarly to the above process and / or according to the general preparation, compounds of the general formula (XXIII) are obtained:

Table 6

Example (XIV-1)

At 70 ° C., 99.3 g of 2-chloro-4-ethylphenylacetic acid and 109 ml (1.5 mol) of thionyl chloride were stirred until gas evolution ceased. Excess thionyl chloride was removed at 50 ° C. under reduced pressure. The residue was distilled off.

Yield: 99.10 g (91% of theory), boiling point: 121 ° C./0 to 35 mbar.

Example (XVII-1)

102.5 g (16.9% strength, 0.05 mol) of compound of Example (XVIII-1), 14.1 g KOH, 17.8 mL water and 35.5 mL methanol were heated together at reflux for 5 hours. Then the mixture was concentrated and the residue was dissolved in water. The solution was washed with ethyl acetate and the aqueous phase was acidified with concentrated HCl (pH 1). The precipitate was filtered off with suction and dried.

Yield: 14.4 g (80.6% of theory), Melting point: 140 to 142 ° C.

Similarly to the above process and / or according to the general preparation, compounds of the general formula (XVII) are obtained:             

TABLE 7

Example (XVIII-1)

While cooling, 9.1 ml of 30% strength sodium methoxide was added dropwise to 5 g (94.4% strength, 0.0119 mol) of Example (XIX-1) in 5 ml of methanol, and the mixture was stirred at reflux for 5 hours. After cooling, 0.01 ml of concentrated sulfuric acid was added dropwise and the mixture was stirred at reflux for 1 hour. Then the mixture was concentrated and the residue was dissolved in water. The solution was extracted with methylene chloride, dried and concentrated.

Yield: 1.80 g (43% of theory), oil.

Similarly to the above process and / or according to the general preparation, compounds of the general formula (XVIII) are obtained:

Table 8

^* After chromatographic purification, to give the acid of formula (XVII-6) and (XVII-7) that corresponds to the direct reaction of these compounds.

Example (XIX-1)

To 208 ml (1.746 mol) of butyl nitrite in 684 ml of anhydrous acetonitrile 1400 ml (17.4 mol) of 1,1-dichloroethane followed by 320 g (1.147 mol) of the compound of Example (XX-1) in 342 ml of anhydrous acetonitrile ) Was added dropwise. The mixture was stirred overnight at room temperature and then poured into 4.6 L of 20% strength HCl. After the mixture was extracted with MTB ether, the organic phase was washed with 2 liters of water, dried and concentrated.

Yield 434 g.

The crude product was further reacted without further purification.

Similarly to the above process and / or according to the general preparation, compounds of the general formula (XIX) were obtained:

Table 9

^The crude mixture was used directly for alcoholysis to prepare compounds of general formula (XVIII).

Example (XX-1)

At 10 to 30 ° C., 397 g (2.48 moles) of bromine in 744 ml of glacial acetic acid were added dropwise to 150 g (1.24 moles) of 4-ethylaniline in 1990 ml of glacial acetic acid, and the mixture was stirred at 30 ° C. for 3 hours. The mixture was then diluted with water and made alkaline using 25% strength ammonia solution. The precipitate was suction filtered to dissolve in methylene chloride, then dried and concentrated.

Yield: 320.0 g (93% of theory), Melting point: 74 ° C.

Example (XX-2)

Using the method of Example (XX-1), a compound of the following structural formula was obtained:

Melting point: 48 ° C.

Example (XXII-1)

At room temperature, 30.5 g (0.27 mol) of 2-methyl-tetrahydropyran-4-one (see later for preparation example) was added 15.7 g (0.32 mol) of sodium tetrachloride in 48 ml of water, 17.2 g (0.32 mol) of ammonium chloride And 50.9 g (0.75 mol) of 25% strength ammonia solution dropwise, and the mixture was stirred at 45 ° C. overnight. Post-treatment in the usual manner gave 29.1 g (77% of theory) of the final product as an oil.

Example (XXII-2)

In a similar manner the compound was obtained as a brown oil.

Example Compounds of the Structural Formula

At a temperature of about 100 ° C., 364.37 g of the compound of the formula ClCH ₂ CH ₂ COCH ₂ CHClCH ₃ (preparation examples are shown in the following examples) was added 179.7 g (1.55 mol) of 85% strength o-phosphate in 5500 mL of water and NaH ₂ PO 552.72 g (3.54 mole) of ₄ × 2H ₂ O was added dropwise over about 75 minutes, and the mixture was stirred at 100 ° C. for 8 hours.

The mixture was cooled to about 0 ° C and 10 molar NaOH was added dropwise until the pH was 5-6. 1500 ml of methylene chloride were added and the resulting salt was filtered off with suction to extract the aqueous phase three times with 1000 ml of methylene chloride each time. The organic phase is dried, concentrated and distilled off.

Yield: 119.6 g (55% of theory), boiling point: 62 ° C./15 mbar.

EXAMPLES Compounds of Structural Formula ClCH ₂ CH ₂ COCH ₂ CHClCH ₃

At room temperature, 507.88 g of 3-chloropropionyl chloride was added dropwise to 758.08 g (5.6 mol) of AlCl ₃ in 560 ml of methylene chloride over 15 minutes, and 189 g (4.5 mol) of propylene was added at about 28 to 30 ° C. Introduced over about 3 hours.

The reaction mixture was decanted from excess AlCl ₃ and slowly added dropwise to a mixture of 508 mL of methylene chloride and 2032 mL of 1N HCl at 0-10 ° C.

The organic phase was separated and washed three times with 500 ml of water each time, then dried and concentrated.

Yield: 470 g (70% of theory).

Example of use

Example A

Miss Juice Test

Solvent: Dimethylformamide 7 parts by weight

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

1 part by weight of the active compound is mixed with the specified amount of solvent and the specified amount of emulsifier and the concentrate is diluted with water to the desired concentration to prepare a suitable formulation of the active compound.

Cabbage leaves ( Brassica oleracea ) heavily infected with peach aphids ( Misso Pacifica ) were treated by dipping into active compound formulations of the desired concentration.

After a certain period of time, the percent rescued was determined. 100% means that all the aphids have been killed; 0% means that the aphid is not killed at all.

In this test, for example, Examples Ia-9, Ia-10, Ia-12, Ia-14, Ia-15, Ia-16, Ic-8, Ib-17, Ia-18, Ia-19, Ia Compounds of -20, Ia-21, Ic-11 and Ic-12 showed a 100% rescue after 6 days at typical active compound concentrations of 0.1% in each case.

Example B

Nepotetics test

Solvent: 20 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

1 part by weight of the active compound is mixed with the specified amount of solvent and the specified amount of emulsifier and the concentrate is diluted with water to the desired concentration to prepare a suitable formulation of the active compound.

Rice hair ( Oryyzae sativa ) was treated by immersion in the active compound formulation of the desired concentration and infected with a cicadas (nepotetics synthiceps) while the hair was moist.

After a certain period of time, the percent rescued was determined. 100% means that all the cicadas have been killed; 0% means that the tarnabis did not die at all.

In this test, for example, Examples Ib-2, Ib-4, Ic-3, Ib-5, Ib-1, Ic-1, Ib-6, Ib-7, Ic-4, Ia-7, Ib Typical active compound concentrations of -8, Ib-11, Ic-5, Ic-7, Ib-17, Ic-11, Ia-22, Ib-22, Ib-23 and Ib-24 are 0.1% in each case In 6 days, a 100% relief rate was shown.

Example C

Phaedon Larva Test             

Solvent: Dimethylformamide 7 parts by weight

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

1 part by weight of the active compound is mixed with the specified amount of solvent and the specified amount of emulsifier and the concentrate is diluted with water to the desired concentration to prepare a suitable formulation of the active compound.

Cabbage leaves (Brassica oleracea) were treated by immersion in the active compound formulation at the desired concentration and infected with mustard beetle (Phaedon cocicleae) larva while the leaves were damp.

After a certain period of time, the percent rescued was determined. 100% means that all the scarab larvae have been killed; 0% means that the scarab larvae are not killed at all.

In this test, for example, compounds of Examples Ib-8, Ib-22, Ib-23, Ic-13, Ib-4, Ic-3, Ia-7 and Ia-8 have a typical activity of 0.1% in each case After 7 days at the compound concentration, 100% remission was shown.

Example D

Spodoptera prugiferda test

Solvent: Dimethylformamide 7 parts by weight

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

1 part by weight of the active compound is mixed with the specified amount of solvent and the specified amount of emulsifier and the concentrate is diluted with water to the desired concentration to prepare a suitable formulation of the active compound.

Cabbage leaves (Brassica oleracea) were treated by immersion in the active compound formulation of the desired concentration and infected with owlet moth ( Spodoptera frugiperda ) caterpillars while the leaves were moist.

After a certain period of time, the percent rescued was determined. 100% means that all caterpillars have been killed; 0% means that the caterpillar was not killed at all.

In this test, for example, the compounds of Examples Ic-3, Ia-14, Ic-15, Ia-20, Ic-13 and Ib-24 are 100% after 7 days at a typical active compound concentration of 0.1% in each case The rescue rate of was shown.

Example E

Tetranicus Test (OP-Resistant / Immersed)

Solvent: 3 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

1 part by weight of the active compound is mixed with the specified amount of solvent and the specified amount of emulsifier and the concentrate is diluted with water containing the emulsifier to the desired concentration to prepare a suitable formulation of the active compound.

Soybean plants (Paceolus vulgaris ) heavily infected with greenhouse red spider mites (Tetranicus urticae) at all stages were immersed in the active compound preparation at the desired concentration.

After a certain period of time, the percent rescued was determined. 100% means that all spider mites have been killed; 0% means that the spider mites are not killed at all.

In this test, for example, Examples Ib-2, Ib-3, Ib-4, Ic-3, Ia-4, Ic-1, Ib-7, Ic-4, Ia-7, Ia-9 and Ib Compounds of -8 showed 100% remission after 14 days at typical active compound concentrations of 0.1% in each case, compounds of Examples Ib-15, Ib-16, Ib-17, Ib-22 and Ic-13 Shows a 100% rescue rate at a typical active compound concentration of 0.02%.

Example F

Critical concentration test / root-systemic action

Test Insect: Apis Pava

Solvent: 4 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

1 part by weight of the active compound is mixed with the specified amount of solvent and the specified amount of emulsifier and the concentrate is diluted with water containing the emulsifier to the desired concentration to prepare a suitable formulation of the active compound.

The active compound preparation was mixed well with the soil. The concentration of active compound in the formulation is of no practical importance, only the amount of active compound per soil volume given in ppm (= mg / L) is critical. The treated soil was transferred to pots and planted with pre-germinated peaches. In this case, the active compound can be absorbed from the soil into the roots of the plant and transferred to the leaves.

To demonstrate the root-systemic effect, after 7 days the leaves were infected with the test animals mentioned above. After 6 days, the number of dead animals was counted or measured. Root-systemic function of the active compound was inferred from the mortality level. 100% means that all test animals have died and 0% means that test insects survive as much as untreated controls.

In this test, for example, Examples Ia-1, Ib-4, Ia-4, Ib-5, Ia-16, Ib-1, Ib-3, Ic-1, Ic-2, Ib-17, Ib Compounds of -10, Ia-16 and Ib-25 showed a 100% effect in each case at a typical active compound concentration of 20 ppm.

Example G

Critical concentration test / root-systemic action

Test Insect: Misso Persia

Solvent: 4 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

1 part by weight of the active compound is mixed with the specified amount of solvent and the specified amount of emulsifier and the concentrate is diluted with water containing the emulsifier to the desired concentration to prepare a suitable formulation of the active compound.             

The active compound preparation was mixed well with the soil. The concentration of active compound in the formulation is of no practical importance, only the amount of active compound per soil volume given in ppm (= mg / L) is critical. The treated soil was transferred to pots and planted with cotyledon pepper. In this case, the active compound can be absorbed from the soil into the roots of the plant and transferred to the leaves.

To demonstrate the root-systemic effect, after 7 days the leaves were infected with the test animals mentioned above. After 6 days, the number of dead animals was counted or measured. Root-systemic function of the active compound was inferred from the mortality level. 100% means that all test animals have died and 0% means that test insects survive as much as untreated controls.

In this test, for example, the compounds of Examples I-b-10, I-a-16 and I-b-25 showed 100% effect at typical active compound concentrations of 20 ppm in each case.

Claims (17)

Compound of Formula (I):

In the above formula, W represents hydrogen, halogen, or C ₁ -C ₆ -alkyl, X represents halogen, C ₁ -C ₆ -alkyl, or cyano, Y represents hydrogen, halogen, C ₁ -C ₆ -alkyl, or cyano, Z represents hydrogen, halogen, or C ₁ -C ₆ -alkyl, A represents C ₁ -C ₆ -alkyl, B represents hydrogen or C ₁ -C ₆ -alkyl, G represents hydrogen (a) or one of the following radicals:

From here, L represents oxygen or sulfur, M represents oxygen or sulfur, R ¹ represents C ₁ -C ₂₀ -alkyl or C ₂ -C ₂₀ -alkenyl, or a 5- or 6-membered heteroaryl having one or two hetero atoms selected from the group consisting of oxygen, sulfur and nitrogen Indicate, R ² represents C ₁ -C ₂₀ -alkyl. delete The method of claim 1, W represents hydrogen, fluorine, chlorine, bromine or C ₁ -C ₄ -alkyl, X represents fluorine, chlorine, bromine, C ₁ -C ₄ -alkyl, or cyano, Y represents hydrogen, fluorine, chlorine, bromine, C ₁ -C ₄ -alkyl, or cyano, Z represents hydrogen, fluorine, chlorine, bromine or C ₁ -C ₄ -alkyl, A represents C ₁ -C ₄ -alkyl, B represents hydrogen, methyl or ethyl, G represents hydrogen (a) or one of the following radicals:

From here, L represents oxygen or sulfur, M represents oxygen or sulfur, R ¹ represents C ₁ -C ₁₆ -alkyl or C ₂ -C ₁₆ -alkenyl, or represents thienyl, R ² is a compound of formula (I) representing C ₁ -C ₁₆ -alkyl. The method of claim 1, W represents hydrogen, fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl, or isobutyl, X represents fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or cyano, Y represents hydrogen, fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, or cyano, Z represents hydrogen, fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or t-butyl, A represents methyl or ethyl, B represents hydrogen or methyl, G represents hydrogen (a) or one of the following radicals:

From here, L represents oxygen or sulfur, M represents oxygen or sulfur, R ¹ represents C ₁ -C ₁₄ -alkyl or C ₂ -C ₁₄ -alkenyl, or represents thienyl, R ² is a compound of formula (I) representing C ₁ -C ₁₄ -alkyl. (A) Intramolecular condensation of the compound of general formula (II) in the presence of a diluent and in the presence of a base to give a compound of general formula (Ia), and optionally, of the obtained general formula (Ia) Compound, (B) optionally in the presence of a diluent and optionally in the presence of an acid binder     α) reacts with an acyl halide of formula (III), or     β) reacts with the carboxylic anhydride of formula (IV), or (C) optionally reacting with a chloroformic ester or chloroformic thioester of general formula (V) in the presence of a diluent and optionally in the presence of an acid binder, (D) optionally reacting with a chloromonothioformic ester or chlorodithioformic ester of formula (VI) in the presence of a diluent and optionally in the presence of an acid binder Method for preparing the compound of (I):

Where A, B, W, X, Y, Z, R ¹ , R ² , and M each have the meanings mentioned in claim 1, R ⁸ represents C ₁ -C ₆ -alkyl, Hal represents halogen. Compound of formula (II):

Where A, B, W, X, Y and Z are each as defined in claim 1, R ⁸ represents C ₁ -C ₆ -alkyl. Compound of general formula (XIII):

Where A and B are each as defined in claim 1, R ⁸ represents C ₁ -C ₆ -alkyl. Compound of general formula (XV):

Where A, B, W, X, Y and Z are each as defined in claim 1. Compound of general formula (XVI):

Where A and B are each as defined in claim 1. Compound of general formula (XXII):

Where A and B are each as defined in claim 1. Compound of general formula (XXIII):

Where A, B, X, Y, Z and W are each as defined in claim 1. Compound of formula (XVII):

Where X ¹ represents fluorine, chlorine or bromine, Y ¹ represents ethyl, W ¹ represents hydrogen, fluorine, chlorine or bromine. Compound of formula (XVIII):

Where X ¹ , Y ¹ and W ¹ are each as defined in claim 12, R ⁸ represents C ₁ -C ₆ -alkyl. A pesticide or herbicide characterized by containing a compound of formula (I) according to claim 1. delete A method of controlling pests and weeds, characterized in that the compounds of formula (I) according to claim 1 are acted on pests or weeds and / or their habitats. A process for preparing pesticides and herbicides, characterized in that the compound of formula (I) according to claim 1 is mixed with an extender and / or a surfactant.